High strain gels, gel composites and artificial muscel actuators made thereform

ABSTRACT

Novel gels and articles are formed from one or more copolymers having at least one poly(ethylene) components and high levels of one or more plasticizers, said gels having an amount of crystallinity, glassy components, and selected plasticizers sufficient to achieve improvements in one or more physical properties including improved crack propagation resistance, improved tear resistance, improved resistance to fatigue, resistance to catastrophic failure, and exhibiting high strain under elongations not obtainable in amorphous gels which high strain making the gel suitable for use as film layers for artificial muscles.

RELATED APPLICATIONS

[0001] This application is a continuation-in-part of the followingapplications: Ser. No. 09/517/230, filed Mar. 2, 2000, Ser. No.09/412,886, filed Oct. 5, 1999, Ser. No. 09/285809, filed Apr. 1, 1999Ser. No. 09/274498, filed Mar. 23, 1999; Ser. No. 08/130,545, filed Aug.8, 1998, Ser. No. 08/984,459, filed Dec. 3, 1997, Ser. No. 08/909,487,filed Jul. 12, 1997; Ser. No. 08/863,794, filed May 27, 1997;PCT/US97/17534, filed Sep. 30, 1997, U.S. Ser. No. 08/719,817 filed Sep.30, 1996, U.S. Ser. No. 08/665,343 filed Jun. 17, 1996 which is aContinuation-in-part of U.S. Ser. No. 612,586 filed Mar. 8, 1996,PCT/US94/04278 filed Apr. 19, 1994 (published May 26, 1995 No.WO95/13851); PCT/US94/07314 filed Jun. 27, 1994 (published Jan. 4, 1996No. WO 96/00118), Ser. No. 288,690 filed Aug. 11, 1994, Ser. No. 581,188filed Dec. 29, 1995, Ser. No. 581,191 filed Dec. 29, 1995 Ser. No.5,81,125 filed Dec. 29, 1995 now U.S. Pat. No. 5,962,527 In turn U.S.Ser. Nos. 581,188; 581,191, and 581,125 (now U.S. Pat. No. 5,962,572)are continuation in-parts of the following applications Ser. Nos.288,690, filed Aug. 11, 1994, PCT/US94/07314 filed Jun. 27, 1994 (CIP ofPCT/US 94/04278, filed Apr. 19, 1994) The subject matter contained inthe related applications and patents are specifically incorporatedherein by reference

FIELD OF THE INVENTION

[0002] The present invention is directed to novel gels, composites andarticles as artificial muscles

BACKGROUND OF THE INVENTION

[0003] There have been many breakthroughs published on the internetincluding muscles made from flexible polymer ribbons constructed fromchains of carbon, fluorine, and oxygen molecules (Yoseph Bar-Cohen @ wwwdiscover com/augustissue/breakbend bots html) Mo Shahinpoor makes hisout of polyacrylonitrile, see www sciamcom/explorations/050596explorationsbox4 html, and a polymer muscleconsists of thin sheets wrapped into a cigarlike cylinder

[0004] Other types of (internet announced) polymer muscle are thinsheets wrapped into a cigarlike cylinder These polymers stretch when oneside of a sheet is given a positive charge and the other a negativeThese charges cause each wrapped sheet to contract toward the center ofthe cylinder, and this construction forces the cylinder to expandlengthwise When the power supply is off, the rope relaxes These polymerscan push, pull, and lift loads

[0005] SRI International is investigating artificial muscle for smallrobots using electrostrictive polymers The muscle has compliantelectrodes on the surface of the polymer film, contracts in thicknessand extends in length and width due to the electrostatic forces when avoltage is applied The polymer enhances the electrostatic force becauseof its dielectric constant The net result is a muscle with a largestrain (>30%) and a large actuation pressure (0.21 MPa in silicon, 1.9MPa in polyurethane) The performance of the artificial muscle iscomparable to the natural muscle, but with higher efficiency and fasterresponse Artificial muscle can be fabricated using spin coating,dipping, or casting Once the muscle is fabricated, it can also be foldedor rolled to make the muscle actuator more compact The artificial muscleactuator shown in FIG. 2 uses a spin coated film which is first foldedthen rolled, followed by folding and to achieve 20 layers The activemuscle for the actuator is 10 mm in length and 3 mm in diameter andgives a maximum stroke of 1 mm and maximum force of 2 grams (2×10⁴ uN)Its weight is approximately 0.1 grams

[0006] The ability to reduce the number of layers and increase themuscle material's strain, thereby greatly reducing the size of theactive muscle actuator and/or increasing the stroke distance at agreater force are challenges not achieved in the prior art

[0007] This application is based upon subject matters described inearlier filed and copending related applications and patents (seeRelated Applications above) which are specifically incorporated hereinby reference

SUMMARY OF THE INVENTION

[0008] I have now discovered novel gels with improved properties madefrom thermoplastic elastomer random copolymers and block copolymershaving one or more polyethylene segment midblocks exhibiting greateradvantage over other non-ethylene component forming gels for makingartificial muscles. The gels advantageously exhibit high tearresistances, high tensile strength and exhibit high strain underelongation. Such gels are advantageous for end-use involving repeatedapplications of stress and strain resulting from large number of cyclesof elongations, deformations, including compression,compression-extension (elongation), torsion, torsion-compression,torsion-elongation, tension, tension-compression, tension-torsion,exhibit high strain under elongation and the like. The gels also exhibitimproved damage tolerance, crack propagation resistance and especiallyimproved resistance to high stress rupture which combination ofproperties makes the gels advantageously and surprisingly exceptionallymore suitable for use as artificial muscles than amorphous gels madefrom non-poly(ethylene) component copolymers at corresponding gel Bloomrigidities.

[0009] The artificial muscle actuators of the invention comprises one ormore thin film layers folded or rolled into the shape of a cylinderforming a center part of said cylinder and an outer part of saidcylinder, said film layer having a top surface and a bottom surface,said top surface and said bottom surface each coated with an electricalconducting layer, said conducting layer of said top surface connected bya first electrode on said top surface positioned at said center part andsaid bottom surface connected by a second electrode on said bottomsurface positioned at said outer part; said first and second electrodesbeing connected to a direct current power source, said power supplycapable of generating a electrical potential of a positive electricalcharge to the first electrode and a negative electrical charge to thesecond electrode of at least about 10,000 volts; said film layerscomprising a gel made from one or more copolymers characterized bysufficient crystallinity as to exhibit a melting endotherm of at leastabout 25° C. as determined by DSC curve, and said gel beingcharacterized by sufficient crystallinity as to exhibit a meltingendotherm of about 25° C., 21° C., 22° C., 23° C., 24° C., 25° C., 26°C., 27° C., 28° C., 29° C., 30° C., 31° C., 32° C., 33° C., 34° C., 35°C., 36° C., 37° C., 38° C., 39° C., 40° C., 41° C., 42° C., 43° C., 44°C., 45° C., 46° C., 47° C., 48° C., 49° C., 50° C., 51° C., 52° C., 53°C., 54° C., 55° C., 56° C., 57° C., 58° C., 59° C., 60° C. or higher asdetermined by differential scanning calorimeter (DSC) curve, said gelhaving rigidities of from less than about 2 gram Bloom to about 1,800gram Bloom; and said gel having sufficient crystallinity so as toexhibit greater strain under elongation than amorphous gels of SEPS andSEBS.

[0010] The usefulness of the gels as artificial muscles is because ofthe inherent crystallinity of one or more components of the copolymersforming the gels which makes the gels useful as artificial muscles. Thecrystallinity provides greater strain under elongation which advantageis surprisingly not found in gels of corresponding gel rigidities madefrom amorphous block copolymers such aspoly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-propylene-styrene), high vinylpoly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-ethylene-butylene-styrene) alone.

[0011] As used herein, the term “gel rigidity” in gram Bloom isdetermined by the gram weight required to depress a gel a distance of 4mm with a piston having a cross-sectional area of 1 square centimeter at23° C. 23° C.

[0012] The various aspects and advantages will become apparent to thoseskilled in the art upon consideration of the accompanying disclosure.

DESCRIPTION OF THE DRAWINGS

[0013]FIG. 1. Representative sectional view of gel, composite and gelarticles useful as artificial muscles.

[0014] FIGS. 2A-2 d. Representative sectional view of gel, composite andgel articles useful as artificial muscles.

[0015] FIGS. 3A-3 n. Representative sectional view of gel, composite andgel articles useful as artificial muscles.

[0016]FIGS. 4a-4 x. Representative sectional view of gel, composite andgel articles useful as artificial muscles.

DESCRIPTION OF THE INVENTION

[0017] Thermoplastic elastomer gels are described in my patents andpublished applications: PCT/US97/17534; PCT/US94/04278; PCT/US94/07314;U.S. Pat. Nos. 5,884,639; 5,868,597; 5,760,117; 5,655,947, 5,624,294;5,508,334; 5,475,890; 5,336,708; 5,324,222; 5,262,468; 5,239,723;5,153,254; 4,618,213; and 4,369,284. Various patents on thermoplasticelastomers and blends are described in U.S. Pat. Nos. 5,755,243;3,595,942, Reissue 27,145-28,236; 3,772,234; 4,116,917; 4,687,815; and4,880,878. Other non-patent publications related to S-EB-S polymersinclude (1) W. P. Gergen, “Uniqueness of Hydrogenated Block Copolymersfor Elastomeric Applications,” presented at the German Rubber Meeting,Wiesbaden, 1983, Kautsch, Gummi, Kunstst. 37, 284 (1984). (2) W. P.Gergen, et al., “Hydrogenated Block Copolymers,” Paper No. 57, presentedat a meeting of the Rubber Division ACS, Los Angeles, Apr. 25, 1985.Encyclopedia of Polymer Science and Engineering, Vol. 2, pp 324-434,“Block Copolymers”. (3) L. Zotteri and et al., “Effect of hydrogenationon the elastic properties of poly(styrene-b-diene-b-styrene)copolymers”, Polymer, 1978, Vol. 19, April. (4) J. Kenneth Craver, etal., Applied Polymer Science, Ch. 29, “Chemistry and Technology of BlockPolymers”, pp 394-429, 1975. (5) Y. Mahajer and et al., “The influenceof Molecular Geometry on the Mechanical Properties of homopolymers andBlock Polymers of Hydrogenated Butadiene and Isoprene” reported underU.S. ARO Grant No. DAAG29-78-G-0201. (6) J E. McGrath, et al., “Linearand Star Branched Butadiene-Isoprene Block Copolymers and TheirHydrogenated Derivatives”, Chem. Dept, Virginia Polytechnic Instituteand State University Blacksturg, Va., reported work supported by ArmyResearch Office. (7) Legge, Norman R., “Thermoplastic Elastomers”,Charles Goodyear Medal address given at the 131st Meeting of the RubberDivision, American Chemical Society, Montreal, Quebec, Canada, Vol. 60,G79-G115, May 26-29, 1987. (8) Falk, John Carl, and et al., “Synthesisand Properties of Ethylene-Butylene-1 Block Copolymers”, Macromolecules,Vol. 4, No. 2, pp. 152-154, March-April 1971. (9) Morton, Maurice, andet al., “Elastomeric Polydiene ABA Triblock Copolymers withinCrystalline End Blocks”, University of Arkon, work supported by GrantNo. DMR78-09024 from the National Science Foundation and ShellDevelopment Co. (10) Yee, A. F, and et al., “Modification of PS byS-EB-S Block Copolymers: Effect of Block Length”, General ElectricCorporate Research & Development, Schenectady, N.Y. 12301. (11)Siegfried, D. L., and et al, “Thermoplastic Interpenetrating PolymerNetworks of a Triblock Copolymer elastomer and an Ionomeric PlasticMechanical Behavior”, Polymer Engineering and Science, January 1981,Vol. 21, No.1, pp 39-46. (12) Clair, D. J., “S-EB-S Copolymers ExhibitImprove Wax Compatibility”, Adhesives Age, November, 1988. (13) ShellChemical Technical Bulletin SC: 1102-89, “Kraton® Thermoplast Rubbers inoil gels”, April 1989 (14) Chung P. Park and George P. Clingerman,“Compatibilization of Polyethylene-Polystyrene Blends withEthylene-Styrene Random Copolymers”, the Dow Chemical Company, May 1996.(15) Steve Hoenig, Bob Turley and Bill Van Volkenburgh, “MaterialProperties and Applications of Ethylene-Styrene Interpolymers”, the DowChemical Company, September 1996. (16) Y. Wilson Cheung and Martin J.Guest, “Structure, Thermal Transitions and Mechanical Properties ofEthylene/Styrene Copolymers”, the Dow Chemical Company, May 1996. (17)Teresa Plumley Karjaia, Y. Wilson Cheung and Martin J. Guest, “MeltRheology and Processability of Ethylene/Styrene Interpolymers”, the DowChemical Company, May 1997. (18) D. C. Prevorsek, et al., “Origins ofDamage Tolerance in Ultrastrong Polyethylene Fibers and Composites:,Journal of Polymer Science: Polymer Symposia No. 75, 81-104 (1993). (19)Chen, H., et al, “Classification of Ethylene-Styrene Interpolymers Basedon Comonomer Content”, J. Appl Polym. Sci., 1998, 70, 109. (20-24) U.S.Pat. Nos. 5,872,201; 5,460,818; 5,244,996; EP 415815A; JP07,278,230describes substantially random, more appropriately presudo-randomcopolymers (interpolymers), methods of making and their uses. (25)Alizadeh, et al., “Effect of Topological Constraints on TheCrystallization Behavior of Ethylene/alp[ha-Olefin Copolymers”, PMSE,Vol, 81, pp. 248-249, Aug. 22-26, 1999. (26) Guest et al.,“Structure/Property Relationships 0f Semi-Crystalline Ethylene-StyreneInterpolymers (ESI)”, PMSE, Vol, 81, pp. 371-372, Aug. 22-26, 1999. Theabove applications, patents and publications are specificallyincorporated herein by reference.

[0018] Legge's paper teaches the development of (conventionalsubstantially amorphous elastomer midsegment) SEBS triblock copolymers.In the polymerization of butadiene by alkylithium initiators,1,4-addition or 1,2-addition polymers, mixtures, can be obtained. Informing styrene butadiene triblock copolymers involving the addition ofsolvating agents such as ethers just before the final styrene charge isadded, any excess of ethers can alter the polybutadiene structure from a1,4-cis or trans structure to a 1,2- or 3,4-addition polymer. Usingdifunctional coupling agent would give linear block copolymers andmultifuntional agents would give star-shaped or radial block copolymers.Hydrogenation of the 1,4-polybutadiene structure yields polyethylene,while that of the 1,2-polybutadiene yields polybutylene. The resultingpolyethylene will be essentially identical with linear, high-densitypolyethylene with a melting point, Tm, of about 136° C. Hydrogenation of1,2-polybutadiene would yield atactic poly(1-butene)(polybutylene). TheTg of polybutylene is around −18° C. Random mixtures of ethylene andbutylene units in the chain would suppress crystallinity arising frompolyethylene sequences. The objective for a good elastomer should be toobtain a saturated olefin elastomeric segment with the lowest possibleTg and the best elastomeric properties. Such an elastomer favored usingstyrene as the hard-block monomer and selecting the best monomer forhydrogenation of the elastomer midsegment. Using a mixture of 1,4- and1,2-polybutadiene as the base polymer for the midsegment would result inan ethylene/butylene midsegment in the final product. The elements ofselection of the midsegment composition is elastomer crystallinity andthe elastomer Tg of an ethylene/butylene copolymer. Very low levels ofcrystallinity can be achieved around 40-50% butylene concentration. Theminimum in dynamic hysteresis around 35% butylene concentration in theelastomeric copolymer. A value of 40% butylene concentration in theethylene/butylene midsegment was chosen for the S-EB-S block copolymers.

[0019] Clair's paper teaches that the EB midblock of conventional S-EB-Spolymers is a random copolymer of ethylene and 1-butene exhibitingnearly no crystallinity in the midblock. In the preparation ofethylene-butylene (EB) copolymers, the relative proportions of ethyleneand butylene in the EB copolymer chain can be controlled over a broadrange from almost all ethylene to almost all butylene. When the EBcopolymer is nearly all ethylene, the methylene sequences willcrystallize exhibiting properties similar to low density polyethylene.In differential scanning calorimeter (DSC) curves, the melting endothermis seen on heating and a sharp crystallization exotherm is seen oncooling. As the amount of butylene in the EB copolymer is increased, themethylene sequences are interrupted by the ethyl side chains whichshorten the methylene sequences length so as to reduce the amount ofcrystallinity in the EB copolymer. In conventional S-EB-S polymers, theamount of 1-butene is controlled at a high enough level to make the EBcopolymer midblock almost totally amorphous so as to make the copolymerrubbery and soluble in hydrocarbon solvents. Clair suggests that anS-EB-S polymer retaining at least some crystallinity in the EB copolymermidblock may be desirable Therefore, a new family of S-EB-S polymers aredeveloped (U.S. Pat. No. 3,772,234) in which the midblock contains ahigher percentage of ethylene. The molecular weights of the ethylenemidblock segment S-EB-S polymers can vary from low molecular weight,intermediate molecular, to high molecular weight; these are designatedShell GR-3, GR-1, and GR-2 respectively. Unexpectly, the highestmolecular weight polymer, GR-2 exhibits an anomalously low softeningpoint. A broad melting endotherm is seen in the DSC curves of thesepolymers. The maximum in this broad endotherm occurs at about 40° C.

[0020] Himes, et al., (U.S. Pat. No. 4,880,878) describes SEBS blendswith improved resistance to oil absorption.

[0021] Papers (14)-(17) describes poly(ethylene-styrene) substantiallyrandom copolymers (Dow Interpolymers™): Dow S, M and E Series producedby metallocene catalysts, using single site, constrained geometryaddition polymerization catalysts resulting in poly(ethylene-styrene)substantially random copolymers with weight average molecular weight(Mw) typically in the range of 1×10⁵ to 4×10⁵, and molecular weightdistributions (Mw/Mn) in the range of 2 to 5

[0022] Paper (18) Prevorsek, et al., using Raman spectroscopy, WAXS,SAXD, and EM analysis interprets damage tolerance of ultrastrong PEfibers attributed to the nano scale composite structure that consists ofneedle-like-nearly perfect crystals that are covalently bonded to arubbery matrix with a structure remarkably similar to the structure ofNACRE of abalone shells which explains the damage tolerance and impactresistance of PE fibers. PE because of its unique small repeating unit,chain flexibility, ability to undergo solid state transformation of thepolyethylene phase without breaking primary bonds, and its low glasstransition temperature which are responsible for large strain rateeffects plays a key role in the damage tolerance and fatigue resistanceof structures made of PE fibers.

[0023] Chen (19) classifies 3 distinct categories of E (approximately20-50 wt % styrene), M (approximately 50-70 wt % styrene), & S (greaterthan approximately 70 wt % styrene) substantially random or moreappropriately pseudo-random ethylene-styrene copolymers or randomcopolymers of ethylene and ethylene-styrene dyads. The designatedEthylene-styrene copolymers are: E copolymers (ES16, ES24, ES27, ES28,ES30, and ES44 with styrene wt % of 15.7, 23.7, 27.3, 28.1, 39.6 & 43.9respectively), M copolymers (ES53, ES58, ES62, ES63, and ES69 withstyrene wt % of 52.5, 58.1, 62.7, 62.8, and 69.2 respectively andcrystallinity, %, DSC, based on copolymer of 37.5, 26.6, 17.4, 22.9,19.6 and 5.0 respectively), S copolymers (ES72, ES73, and ES74 withstyrene wt % of 72.7, 72.8, and 74.3 respectively). The maximumcomonomer content for crystallization of about 20% is similar in otherethylene copolymers, such as in ethylene-hexene and ethylene-vinylacetate copolymers. If the comonomer can enter the crystal lattice, suchas in ethylene-propylene, compositions in excess of 20 mol % comonomercan exhibit crystallinity. The molecular weight distribution of thesecopolymers is narrow, and the comonomer distribution is homogeneous.These copolymers exhibit high ethylene, lamellar morphologies to fringedmicellar morphologies of low crystallinity. Crystallinity is determinedby DSC measurements using a Rheometric DSC. Specimens weighing between 5and 10 mg are heated from −80 to 180° C. at a rate of 10° C./min (firstheating), held at 190° C. for 3 min, cooled to −80° C. at 10° C./min,held at −80° C. for 3 min,and reheated from −80° C. to 180° C. at 10°C./min (second heating). The crystallinity (wt %) is calculated from thesecond heating using a heat of fusion of 290 J/g for the polyethylene.Contributing effects of the crystallinity include decrease volumefraction of the amorphous phase, restricted mobility of the amorphouschain segments by the ethylene domains, and higher styrene content ofthe amorphous phase due to segregation of styrene into the amorphousphase. Table I of this paper shows values of Total Styrene (wt %), aPS(wt %), Styrene (wt %), Styrene (mol %), 10⁻³ Mw, Mw/Mn, and Talc (wt %)for Ethylene-styrene copolymers ES16-ES74 while FIGS. 1-12 of this papershows: (1) melting thermograms of ESI 1st and 2nd heating for ES16,ES27, ES44, ES53, ES63, & ES74; (2) crystallinity from DSC as a functionof conmonomer content; (3) Logarithmic plot of the DSC heat of meltingvs. Mole % ethylene for ESIs; (4) measured density as a function ofstyrene content for semicrystalline and amorphous ESIs; (5) %crystallinity from density vs % crystallinity from DSC melting enthalpy;(6) Dynamic mechanical relaxation behavior; (7) Glass transitiontemperature as a function of wt % ethylene-styrene dyads forsemicrystalline and amorphous ESIs, (8) Arrhenius plots of the losstangent peak temperature for representative semicrystalline andamorphous ESIs; (9) Draw ratio vs engineering strain; (10) Engineeringstress-strain curves at 3 strain rates for ES27, ES63 and ES74; (11)Engineering stress-strain curves of ESIs; (12) Classification scheme ofESIs based on composition.

[0024] (20) U.S. Pat. No. 5,872,201 describes interpolymers, terpolymersof ethylene/styrene/propylene, ethylene/styrene/4-methyl-1-pentene,ethylene/styrene/hexend-1, ethylene/styrene/octene-1, andethylene/styrene/norbornene with number average molecular weight (Mn) offrom 1,000 to 500,000.

[0025] (21-24) U.S. Pat. No. 5,460,818; 5,244,996; EP 41 5815A;JP07,278,230 describes substantially random, more appropriatelypresudo-random copolymers (interpolymers), methods of making and theiruses.

[0026] (25) Alizadeh, et al., find the styrene interpolymers impedes thecrystallization of shorter ethylene crystallizable sequences and thattwo distinct morphological features (lamellae and fringe micellar orclain clusters) are observed in ethylene/styrene (3.4 mol %) as lamellacrystals organized in stacks coexisting with interlamellar bridge-likestructures.

[0027] (26) Guest, et al., describes ethylene-styrene copolymers havingless than about 45 wt % copolymer styrene being semicrystalline, asevidenced by a melting endotherm in DSC testing (Dupont DSC-901, 10°C./min) data from the second heating curve. Crystallization decreaseswith increasing styrene content Based on steric hindrance, styrene unitis excluded from the ethylene region of the copolymers. Transition fromethylene to amorphous solid-state occurs at about 45 to 50 wt % styrene.At low styrene contents (<40%), the copolymers exhibit a relativelywell-defined melting process. FIGS. 1-5 of this paper shows (a) DSC datain the T range associated with the melting transition for a range of ESIdiffering primarily in copolymer styrene content, (b) variation inpercent crystallinity (DSC) for ESI as a function of copolymer Scontent, (c) elastic modulus versus T for selected ESI differing in Scontent, (d) loss modulus versus T for selected ESI differing in Scontent, (e) Tensile stress/strain behavior of ESI differing in Scontent, respectively. The above patents and publications arespecifically incorporated herein by reference

[0028] Prior amorphous gels made from SEPS and SEBS are inadequate forthe most demanding applications involving endurance at high stress andstrain levels over an extended period of time exhibiting greater strainunder elongation which are essential for the gels to have uses asartificial muscles.

[0029] The gels which are advantageously useful for making artificialmuscles, toys, medical devices, and other useful articles of manufactureincluding disposable inflatable restraint cushions, and especially foruse as artificial muscles, and the like. Said gels comprises: 100 partsby weight of one or more high viscosity (I) linear triblock copolymers,(II) multi-arm block copolymers, (III) branched block copolymers, (IV)radial block copolymers, (V) multiblock copolymers, (VI) randomcopolymers, (VII) thermoplastic crystalline polyurethane copolymers withhydrocarbon midblocks or mixtures of two or more (I)-(VII) copolymers incombination with or without major or minor amounts of one or more other(VIII) copolymers or polymers, said copolymers having one or moresegments or one or more midblocks comprising one or more polyethylenesegments or midblocks and selected amounts of a compatible plasticizer(IX) sufficient to achieve gel rigidities of from less than about 2 gramBloom to about 1,800 gram Bloom and higher with the proviso that whensaid (I)-(VII) copolymers having nil amorphous segment or nil amorphousmidblock are combined with one or more (VIII) copolymers having one ormore amorphous segments or amorphous midblocks to form a stableplasticizer compatible gel.

[0030] With respect to the random copolymers (VI) embodiments formingthe gels of the invention, such gels comprises:

[0031] (i) one or more substantially random copolymers (pseudo-randomcopolymers or interpolymers) having one or more glassy components and atleast one substantially ethylene components, wherein said (i) copolymersbeing in combination with a selected amount of one or more selectedsecond copolymers comprising:

[0032] (ii) one or more substantially random copolymers having one ormore glassy components and one or more ethylene components of moderatecrystallinity;

[0033] (iii) one or more substantially random copolymers having one ormore glassy components and one or more ethylene components of lowcrystallinity;

[0034] (iv) one or more substantially random copolymers having one ormore glassy components and one or more amorphous components;

[0035] (v) one or more of a diblock, triblock, multi-arm block, branchedblock, radial block, or multiblock copolymers, wherein said (v)copolymers having one or more glassy components and one or moreelastomeric components of selected crystallinity; and

[0036] (vi) one or more of a diblock, triblock, multi-arm block,branched block, radial block, or multiblock copolymers, wherein said(vi) copolymers having one or more glassy components and one or moreamorphous elastomeric components;

[0037] (vii) a mixture of two or more (ii)-(vi) copolymers;

[0038] wherein said (i)-(iii) and (v) copolymers are characterized bysufficient crystallinity as to exhibit a melting endotherm of at leastabout 25° C. as determined by DSC curve, and said gel beingcharacterized by sufficient crystallinity as to exhibit a meltingendotherm of at least about 10° C. as determined by DSC curve;

[0039] (II) in combination with or without one or more of selectedhomopolymers; and

[0040] (III) a selected amount of one or more compatible plasticizers ofsufficient amounts to achieve a stable gel having rigidities of fromless than about 2 gram Bloom to about 1,800 gram Bloom.

[0041] The gels comprising the thermoplastic elastomer copolymers andblock copolymers having one or more polyethylene segments or midblocksof the invention are hereafter referred to as “elastic gels” or simpler“gels”. The crystalline copolymers are characterized by sufficientcrystallinity as to exhibit a melting endotherm of at least about 25° C.as determined by DSC curve, and said gel being characterized bysufficient crystallinity as to exhibit a melting endotherm of at leastabout 10° C. as determined by DSC curve.

[0042] The various types of copolymers and block copolymers employed informing the crystal-gels of the invention are of the generalconfigurations (Y-AY)_(n) copolymers, A-Z-A, and (A-Z)n blockcopolymers, wherein the subscript n is a number of two or greater. Inthe case of multiarm block copolymers where n is 2, the block copolymerdenoted by (A-Z)n is A-Z-A. It is understood that the coupling agent isignored for sake of simplicity in the description of the (A-Z)n blockcopolymers.

[0043] The segment (A) comprises a glassy amorphous polymer end blocksegment which can be polystyrene, poly(alpha-methylstyrene),poly(o-methylstyrenc), poly(m-methylstryene), poly(p-methylstyrene) andthe like, preferably, polystyrene.

[0044] The segment (Y) of copolymers (Y-AY)_(n) comprises poly(ethylene)(simply denoted by “-E-” or (E)). In the case of copolymers (A-Y)_(n),(Y) when next to (A) may be substantially non-ethylene or amorphousethylene segments. For example a polyethylene copolymer (Y-AY)_(n) maybe represented by: . . .-E-E-E-E-E-E-E-E-E-SE-E-E-E-E-E-E-SE-E-E-E-E-E-E-SE- . . . . Where Y isa long run of polyethylene or a non-ethylene copolymer (AY-AY)_(n) . . .-E-SE-SE-E-SE-E-SE-E-SE-E-E-SE-SE-E-SE- . . . where Y is anon-polyethylene run of ethylene.

[0045] Other substantially random copolymers suitable for forming gelsof the invention include (Y-A-Y′) where Y is a polyethylene run ofethylene and Y′ can be propylene, 4-methyl-1-pentene, hexene-1,octene-1, and norborene. A can be styrene, vinyl toluene,alpha-methylstyrene, t-butylstyrene, chlorostyrene, including isomersand the like. Examples are: poly(ethylene-styrene) (ES),poly(ethylene-styrene-propylene) (ESP),poly(ethylene-styrene-4-methyl-1-pentene) (ES4M1P),poly(ethylene-styrene-hexend-1) (ESH1), poly(ethylene-styrene-octene-1)(ESO1), and poly(ethylene-styrene-norborene) (ESN),poly(ethylene-alpha-methylstyrene-propylene),poly(ethylene-alpha-methylstyrene-4-methyl-1-pentene),poly(ethylene-alpha-methylstyrene-hexend-1),poly(ethylene-alpha-methylstyrene-octene-1), andpoly(ethylene-alpha-methylstyrene-norborene) and the like.

[0046] The end block segment (A) comprises a glassy amorphous polymerend block segment which can be polystyrene, poly(alpha-methylstyrene),poly(o-methylstyrene), poly(m-methylstryene), poly(p-methylstyrene) andthe like, preferably, polystyrene. The segment (Y) of random copolymersA-Y comprises poly(ethylene) (simply denoted by “-E-” or (E)). In thecase of random copolymers A-Y, (Y) may be substantially non-ethylene oramorphous ethylene segments. The midblocks (Z) comprises one or moremidblocks of poly(ethylene) (simply denoted by “-E- or (E)”) with orwithout one or more amorphous midblocks of poly(butylene),poly(ethylene-butylene), poly(ethylene-propylene) or combination thereof(the amorphous midblocks are denoted by “-B- or (B)”, “-EB- or (EB)”,and “-EP- or (EP)” respectively or simply denoted by “-W- or (W)” whenreferring to one or more of the amorphous midblocks as a group) The Aand Z, and A and Y portions are incompatible and form a two ormore-phase system consisting of sub-micron amorphous glassy domains (A)interconnected by (Z) or (Y) chains. The glassy domains serve tocrosslink and reinforce the structure. The number average molecularweight (Mn) of the random copolymers is preferably greater than 1,000,advantageously from about 5,000 to about 1,100,000, more advantageouslyfrom abut 8,000 to about 700,000. Examples are:

[0047] The method of making Y-A-Y and Y-A-Y′ random copolymers bymetallocene single site catalysts are described in U.S. Pat. Nos.5,871,201, 5,470,993, 5,055,438, 5,057,475, 5,096,867, 5,064,802,5,132,380. 5,189,192, 5,321,106, 5,347,024, 5,350,723, 5,374,696,5,399,635, and 5,556,928, 5,244,996, application EP A-0416815,EP-A-514828, EP-A-520732, WO 94/00500 all of which disclosure areincorporated herein by reference.

[0048] The linear block copolymers are characterized as having aBrookfield Viscosity value at 5 weight percent solids solution intoluene at 30° C. of from less than about 40 cps to about 60 cps andhigher, advantageously from about 40 cps to about 160 cps and higher,more advantageously from about 50 cps to about 180 cps and higher, stillmore advantageously from about 70 cps to about 210 cps and higher, andeven more advantageously from about 90 cps to about 380 cps and higher.

[0049] The branched, star-shaped (radial), or multiarm block copolymersare characterized as having a Brookfield Viscosity value at 5 weightpercent solids solution in toluene at 30° C. of from about 80 cps toabout 380 cps and higher, advantageously from about 150 cps to about 260cps and higher, more advantageously from about 200 cps to about 580 cpsand higher, and still more advantageously from about 100 cps to about800 cps and higher.

[0050] The poly(ethylene/styrene) copolymers, type S series has morethan 50 wt % styrene and is glassy at short times and rubbery at longtimes and exhibits ambient Tg, melt density of about higher than 0.952to about 0.929 and less, typical Mw=about less than 150,000 to 350,000and higher.

[0051] The type M series has more than 50 wt % styrene is amorphousrubber and exhibits very low modulus, high elasticity, low Tg of fromgreater than 10° C. to less than −50° C., melt Index of from higher than5 to less than about 0.1, melt density of higher than 0.93 to 9.0 andless, typical Mw=about less than 200,000 to 300,000 and higher.

[0052] The type E series contains up to 50 wt % styrene issemi-crystalline rubber and exhibits low Tg of from greater than 0° C.to about less than −70, low modulus semi-crystalline, good compressionset, Melt Index of from about higher than 2 to less than 0.03, meltdensity of about higher than 0.90 to 0.805 and less, Mw=about less than250,000 to 350,000 and higher.

[0053] The E series random copolymers can be blended with the type M andtype S series copolymers (having high glassy components) and one or moreof the i, ii, iii, iv, v, vii and viii copolymers, plasticizers to formcrystalline polymer Gels of the invention.

[0054] This physical elastomeric network structure is reversible, andheating the polymer above the softening point of the glassy domainstemporarily disrupt the structure, which can be restored by lowering thetemperature. During mixing and heating in the presence of compatibleplasticizers, the glassy domains (A) unlock due to both heating andsolvation and the molecules are free to move when shear is applied. Thedisruption and ordering of the glassy domains can be viewed as aunlocking and locking of the elastomeric network structure. Atequilibrium, the domain structure or morphology as a function of the (A)and (Z) or (A) and (Y) phases (mesophases) can take the form of spheres,cylinders, lamellae, or bicontinous structures. The scale of separationof the phases are typically of the order of hundreds of angstroms,depending upon molecular weights (i.e. Radii of gyration) of theminority-component segments. At such small domain scales, when the gelis in the molten state while heated and brought into contact to beformed with any substrate and allowed to cool, the glassy domains of thegel become interlocked with the surface of the substrate. Atsufficiently high enough temperatures, with or without the aid of otherglassy resins, the glassy domains of the copolymers forming the gelsfusses and interlocks with even a visibly smooth substrate surface suchas glass. The disruption of the sub-micron domains due to heating abovethe softening point forces the glassy domains to open up, unlocking thenetwork structure and flow. Upon cooling below the softing point theglassy polymers reforms together into sub-micron domains, locking into anetwork structure once again, resisting flow. It is this unlocking andlocking of the network structure on the sub-micron scale with thesurfaces of various materials which allows the gel to form interlockingcomposites with other materials. Such interlocking with many differentmaterials produce gel composites having many uses.

[0055] The (I) linear block copolymers are characterized as having aBrookfield Viscosity value at 5 weight percent solids solution intoluene at 30° C. of from less than about 40 cps to about 60 cps andhigher, advantageously from about 40 cps to about 160 cps and higher,more advantageously from about 50 cps to about 180 cps and higher, stillmore advantageously from about 70 cps to about 210 cps and higher, andeven more advantageously from about 90 cps to about 380 cps and higher.

[0056] The (II, IV, and V) branched, star-shaped (radial), or multiarmblock copolymers are characterized as having a Brookfield Viscosityvalue at 5 weight percent solids solution in toluene at 30° C. of fromabout 80 cps to about 380 cps and higher, advantageously from about 150cps to about 260 cps and higher, more advantageously from about 200 cpsto about 580 cps and higher, and still more advantageously from about100 cps to about 800 cps and higher.

[0057] The gels can be made in combination with a selected amount of oneor more selected polymers and copolymers (II) including thermoplasticcrystalline polyurethane elastomers with hydrocarbon blocks,homopolymers, copolymers, block copolymers, polyethylene copolymers,polypropylene copolymers, and the like described below.

[0058] The gels of the invention are also suitable in physicallyinterlocking or forming with other selected materials to form compositescombinations. The materials are selected from the group consisting ofpaper, foam, plastic, fabric, metal, metal foil, concrete, wood, glass,various natural and synthetic fibers, including glass fibers, ceramics,synthetic resin, and refractory materials.

[0059] The high tear resistant soft gels are advantageously suitable fora safer impact deployable air bag cushions, the higher tear resistantgels are advantageously more suitable, and the highest tear resistantgels are advantageously even more suitable for such use and other uses.As impact deployable air bag cushions under expansion exhibit greaterstrain, the greater strain property makes also a better artificialmuscle.

[0060] Very thin films of the gels of the invention are suitable for useas artificial muscles in the form of thin films wrapped into a cylinder.The gel film stretch when one side of a film is given a positive chargeand the other a negative. The charges cause each wrapped film tocontract toward the center of the cylinder which forces the cylinder toexpand lengthwise. When the power supply is off, the cylindrical musclesrelaxes. Thus, the roll up gel can push, pull, and lift loads.

[0061] A thin films or membrane of the gels having a thickness of about5 mm to less than 0.1 mm are useful as artificial muscles. Filmthickness of from 0.005 mm, 0.01 mm, 0.02 mm, 0.03 mm, 0.04 mm, 0.05 mm,0.06 mm, 0.07 mm, 0.08 mm, 0.09 mm, 0.10 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4mm, 1.5 mm, 1.6 mm, 1.7 mm, 1.8 mm, 1.9 mm, 2.0 mm, 2.1 mm, 2.2 mm, 2.3mm, 2.4 mm, 2.5 mm, 2.6 mm, 2.7 mm, 2.8 mm, 2.9 mm, 3.0 mm, 3.1 mm, 3.2mm, 3.3 mm, 3.4 mm, 3.5 mm, 3.6 mm, 3.7 mm, 3.8 mm, 3.9 mm, 4.0 mm canbe utilized for forming artificial muscles of the invention.

[0062] Fine powder of the common transition metals can be utilized as acoating electrodes on the top and bottom flat sides of the gel film toserve as conductor, such as aluminum, alpha aluminum, copper, silver,gold, tin, nickel, iron, cobalt, zinc, lead, and the like.

[0063] We denote “|” as a gel film layer, G, and “∥” as two gel filmlayers, GG, side by side, “|∥” as three gel film layers, GGG, side byside. We denote E as a metal electrode or conductor electrode on bothsides of the G film layer, such as EGE, EGEGE, EGEGEGE, EGEGEGEGE andthe like. We denote (+) as a positive charge, (−) as a negative charge.We then denote the single charged membrane or film layer as “(+)E|E(−)”showing a single gel layer with electrodes on both sides and a positivecharge on its left side and a negative charge on its right side. Hence“(+)E|E(−)(−)E|E(+)”, denotes a double gel thin film layers withelectrodes on each side of the film layers and charged from left toright as positive, negative, negative, and positive. This arrangementallows for the rolling up of the double layers into a cylindricalcylinder without discharging the double layers by rolling unto itself.Another way of rolling up a thin gel film “(+)E|E(−)” require foldingthe (−) side with the (−) sides as a continuous S curve layers uponlayers and then rolling the S curve so that the same charged sides rollunto itself into a cylinder. Other combination can be made for use ascharged thin film layers for artificial muscle use, such as

[0064] a) (+)E|E(−),

[0065] b) (+)E|E(−)(−)E|E(+),

[0066] c) (+)E|E(−)(−)E|E(+)(+)E|E(−),

[0067] d) (+)E|E(−)(−)E|E(+)(+)E|E(−)(−)E|E(+), and

[0068] e) (+)E|E(−)(−)E|E(+)(+)E|E(−)(−)E|E(+)(+)E|E(−).

[0069] Moreover, the gels films can be formed as composite multiplelayers of films with separating electrical conducting layer withencapsulated connectors for easy folding.

[0070] The diameter of the rolled up gel cylinder can be from about 1 mmto abut 8 mm, suitably, about 0.5 mm to about 5 mm, more suitably about1 mm to about 3 mm Generally the rolled up diameter can be from lessthan 0.5 mm to about 12 mm or larger. The length of the cylinder can bealmost any suitable length, from about 5 mm to about 50 mm, suitably, 8mm to 20 mm, more suitably from less than 8 mm to 12 mm and longer.

[0071] Conductive connectors (of foil, polymer, or conductive gel) canbe attached to the inner and outer electrodes respectively. The directcurrent voltage from a regulated power supply or predetermined voltagepositive or negative protental source can be applied which voltage canrange from less than 100 volts to greater than 10,000 volts. Voltages of1,000 v, 2,000 v, 3,000 v, 4,000 v, 5,000 v, 6,000 v, 7,000 v, 8,000 v,9,000 v, 10,000 v, 12,000 v, 15,000 v, 18,000 v can also be used. Thevoltages can be regulated selectively by hand or an electronic timerfrom less than one thousands of a second to minutes, hours, and daysduration. Electrical timing of the applied voltages can range from a fewmicro seconds and longer.

[0072] The gel film can be made by conventional extrusion, hot melt spincoating, casting, dipping and the like. The artificial muscle made inthis manner are useful as contractible muscle elements for small robotswhich gel film, contracts in thickness and extends in length and widthdue to the electrostatic forces when a voltage is applied. The gelcylinder increases and decreases in volume thickness so as to expand andcontract lengthwise due to the electrostatic forces of the charges onthe opposite dielectric surfaces of the gel film. This effect is afunction of the dielectric constant of the gel. In order to provide fora muscle with a large strain and therefore a large actuation pressure(greater than 5 MPa). The performance, efficiency and faster response ofthe cylindrical muscle depends on the amount of strain obtained underelongation. The higher strain under elongation, the better theperformance, the better the efficiency, and the faster the response.

[0073] Gel muscles actuators made from thin films having greaterpolyethylene crystallinity are found to produces greater performance,greater efficiency, and faster response than amorphous gels. This resultis due to the greater strain performance under elongation. Theelongation of the gels of the invention can range from about 100% togreater than 3,000%. The actuation pressure of the actuators made fromthe gels of the invention can range from about 5 MPa to greater thanabout 12 MPa. As an example, a 15 layer rolled/folded gel film actuatorhaving a active muscle length of 10 mm and a diameter of 3 mm (made from0.5 mm thick SEEPS 500 gram Bloom gel) can achieve a stroke of at leastabout 3 mm and a force of at least about 5 grams.

[0074] The strain under elongation of the copolymers forming the gelscan range from less than 8 MPa to about 18 MPa and higher as measure ata strain rate of 1000%/min., from less than 5 MPa to about 25 MPa andhigher as measure at a strain rate of 100%/min., and from less than 5MPa to about 30 MPa and higher as measure at a strain rate of 10%.min.Reference (19) reports the fracture strain % and corresponding modulus(Mpa) for Ethylene-styrene copolymers ES16, ES24, ES27, ES28, ES28, andES30 are 666/52.5, 517/26.4, 453/25, 564/19.5 and 468/25.4 respectively.

[0075] The ability to reduce the number of layers, increase strain withelongation, reduce the size of the active muscle actuator and increasethe stroke distance at a greater force can be achieved with gels(exhibiting high strain under elongation) made from copolymers havingone or more polyethylene components.

[0076] The gels of the invention can be formed into gel strands, geltapes, gel sheets, films, and other articles of manufacture incombination with or without other substrates or materials such asnatural or synthetic fibers, multifibers, fabrics, films and the like.Moreover, because of their improved tear resistance and resistance tofatigue, the gels exhibit versatility as balloons for medical uses, suchas balloon for valvuloplasty of the mitral valve, gastrointestinalballoon dilator, esophageal balloon dilator, dilating balloon catheteruse in coronary angiogram and the like. Since the gels are more tearresistant, they are especially useful for making condoms, toy balloons,and surgical and examination gloves. As toy balloons, the gels are saferbecause it will not rupture or explode when punctured as would latexballoons which often times cause injures or death to children by chokingfrom pieces of latex rubber. The gels are advantageously useful formaking gloves, thin gloves for surgery and examination and thickergloves for vibration damping which prevents damage to blood capillariesin the fingers and hand caused by handling strong shock and vibratingequipment. The gels are also useful for forming orthotics and prostheticarticles such as for lower extremity prosthesis described below.

[0077] The EB copolymer midblock of conventional SEBS is almost totallyamorphous and the EP midblock of SEPS is amorphous and non-ethylene.

[0078] Gels made from such block copolymers are rubbery and exhibitsubstantially no hysteresis. Their rubbery-ness and lack of hysteresisare due to the amorphous nature of their midblocks. Such gels arehereafter referred to as “non-ethylene gels” or more simply as“amorphous gels”.

[0079] In general, the overall physical properties of amorphous gels arebetter at higher gel rigidities The amorphous gels, however, can failcatastrophically when cut or notched while under applied forces of highdynamic and static deformations, such as extreme compression, torsion,high tension, high elongation, and the like. Additionally, thedevelopment of cracks or crazes resulting from a large number ofdeformation cycles can induce catastrophic fatigue failure of amorphousgel composites, such as tears and rips between the surfaces of theamorphous gel and substrates or at the interfaces of interlockingmaterial(s) and gel. Consequently, such amorphous gels are inadequatefor the most demanding applications involving endurance at high stressand strain levels over an extended period of time.

[0080] This physical elastomeric network structure is reversible, andheating the polymer above the softening point of the glassy domainstemporarily disrupt the structure, which can be restored by lowering thetemperature. During mixing and heating in the presence of compatibleplasticizers, the glassy domains (A) unlock due to both heating andsolvation and the molecules are free to move when shear is applied. Thedisruption and ordering of the glassy domains can be viewed as aunlocking and locking of the elastomeric network structure. Atequilibrium, the domain structure or morphology as a function of the (A)and (Z) or (A) and (Y) phases (mesophases) can take the form of spheres,cylinders, lamellae, or bicontinous structures. The scale of separationof the phases are typically of the order of hundreds of angstroms,depending upon molecular weights (i.e. Radii of gyration) of theminority-component segments. The sub-micron glassy domains whichprovides the physical interlocking are too small to see with the humaneye, too small to see using the highest power optical microscope andonly adequately enough to see using the electron microscope. At suchsmall domain scales, when the gel is in the molten state while heatedand brought into contact to be formed with any substrate and allowed tocool, the glassy domains of the gel become interlocked with the surfaceof the substrate. At sufficiently high enough temperatures, with orwithout the aid of other glassy resins (such as polystyrene homopolymersand the like), the glassy domains of the copolymers forming the gelsfusses and interlocks with even a visibly smooth substrate surface suchas glass. The disruption of the sub-micron domains due to heating abovethe softening point forces the glassy domains to open up, unlocking thenetwork structure and flow. Upon cooling below the softing point, theglassy polymers reforms together into sub-micron domains, locking into anetwork structure once again, resisting flow. It is this unlocking andlocking of the network structure on the sub-micron scale with thesurfaces of various materials which allows the gel to form interlockingcomposites with other materials.

[0081] A useful analogy is to consider the melting and freezing of awater saturated substrate, for example, foam, cloth, fabric, paper,fibers, plastic, concrete, and the like. When the water is frozen, theice is to a great extent interlocked with the substrate and upon heatingthe water is able to flow. Furthermore, the interlocking of the ice withthe various substrates on close examination involves interconnecting icein, around, and about the substrates thereby interlocking the ice withthe substrates. A further analogy, but still useful is a plant or weedwell established in soil, the fine roots of the plant spreads out andinterconnects and forms a physical interlocking of the soil with theplant roots which in many instances is not possible to pull out theplant or weed from the ground without removing the surrounding soilalso.

[0082] Likewise, because the glassy domains are typically about 200Angstroms in diameter, the physical interlocking involve domains smallenough to fit into and lock with the smallest surface irregularities, aswell as, flow into and flow through the smallest size openings of aporous substrate. Once the gel comes into contacts with the surfaceirregularities or penetrates the substrate and solidifies, it becomesdifficult or impossible to separate it from the substrate because of thephysical interlocking. When pulling the gel off a substrate, most oftenthe physically interlocked gel remains on the substrate. Even a surfacewhich may appear perfectly smooth to the eye, it is often not the case.Examination by microscopy, especially electron microscopy, will showserious irregularities. Such irregularities can be the source ofphysical interlocking with the gel.

[0083] Such interlocking with many different materials produce gelcomposites having many uses. The high tear resistant soft gels areadvantageously suitable for a safer impact deployable air bag cushions,other uses include: toys; games; novelty, or souvenir items; elastomericlenses, light conducing articles, optical fiber connectors; athletic andsports equipment and articles; medical equipment and articles includingderma use and for the examination of or use in normal or natural bodyorifices, health care articles; artist materials and models, specialeffects; articles designed for individual personal care, includingoccupational therapy, psychiatric, orthopedic, podiatric, prosthetic,orthodontic and dental care; apparel or other items for wear by and onindividuals including insulating gels of the cold weather wear such asboots, face mask, gloves, full body wear, and the like have as anessential, direct contact with the skin of the body capable ofsubstantially preventing, controlling or selectively facilitating theproduction of moisture from selected parts of the skin of the body suchas the forehead, neck, foot, underarm, etc; cushions, bedding, pillows,paddings and bandages for comfort or to prevent personal injury topersons or animals; housewares and luggage; articles useful intelecommunication, utility, industrial and food processing, and the likeas further described herein.

[0084] Health care devices such as face masks for treatment of sleepdisorder require non-tacky gels of the invention. The gel 3 forming agel overlap 7 portion on the face cup 1 at its edge 12 conforming to theface and serve to provide comfort and maintain partial air or oxygenpressure when worn on the face during sleep. Tacky gels because of itstactile feel are undesirable for such applications.

[0085] The gels of the invention can be formed into gel strands, gelbands, gel tapes, gel sheets, and other articles of manufacture incombination with or without other substrates or materials such asnatural or synthetic fibers, multifibers, fabrics, films and the like.Moreover, because of their improved tear resistance and resistance tofatigue, the gels exhibit versatility as balloons for medical uses, suchas balloon for valvuloplasty of the mitral valve, gastrointestinalballoon dilator, esophageal balloon dilator, dilating balloon catheteruse in coronary angiogram and the like. Since the gels are more tearresistant, they are especially useful for making condoms, toy balloons,and surgical and examination gloves. As toy balloons, the gels are saferbecause it will not rupture or explode when punctured as would latexballoons which often times cause injures or death to children by chokingfrom pieces of latex rubber. The gels are advantageously useful formaking gloves, thin gloves for surgery and examination and thickergloves for vibration damping which prevents damage to blood capillariesin the fingers and hand caused by handling strong shock and vibratingequipment. Various other gel articles can be made from theadvantageously tear resistant gels and gel composites of the inventionsinclude gel suction sockets, suspension belts.

[0086] The gels are also useful for forming orthotics and prostheticarticles such as for lower extremity prosthesis described below.

[0087] Advantageously, the gels of the invention can be made non-tackyrequiring no additive. Its non-tackiness are an inherent property of thecrystallinity, glassy A components, and selected low viscosityplasticizers forming the gels of the invention. Such gels, however, mustmet the following criteria:

[0088] (a) the gels are made from A-Z-A, (A-Z)n, (A-Y)n, (Y-AY)n and(Y-AY′)n copolymers: polyethylene block copolymers and crystallinepoly(ethylene-styrene) substantially random copolymers of the type S, M,and E series (for example SEEPS, S-E-EB-S, S-EB₄₅-EP-S, S-E-EB₂₅-S,S-E-EP-E-S, S-EP-E-S, S-EP-E-EP-S, E-S-E, (E-S)n, (E-S-E)n, (ESP),(ES4M1P), (ESH1), (ESO1), (ESN) and (S-E-EP)n, crystalline S-EB-S withelastomeric crystalline block:glassy block ratios of 89:11, 88:12,87:13, 86:14, 85:15, 84:16, 83:17, 82:18, 81:19, 80:20, 79:21, 78:22,77:23, 76:24, 75:25, 74.26, 73:27, 72:28, 71:29, and 70:30) and thelike;

[0089] (b) the gels are made from copolymers having poly(ethylene)segments exhibit melting endotherm values of at least about 25° C., 26°C., 27° C., 28° C., 29° C., 30° C., 31° C., 32° C., 33° C., 34° C., 35°C., 36° C., 37° C., 38° C., 39° C., 40° C., 41° C., 42° C., 43° C., 44°C., 45° C., 46° C., 47° C., 48° C., 49° C., 50° C., 51° C., 52° C., 53°C., 54° C., 55° C., 56° C., 57° C., 58° C., 59° C., 60° C., 61° C., 62°C., 63° C., 64° C., 65° C., 66° C., 67° C., 68° C., 69° C., 70° C., 71°C., 72° C., 73° C., 74° C., 75° C., 76° C., 77° C., 78° C., 79° C., 80°C., and higher; and

[0090] (c) the gels are made from copolymers having glassy A to Y orglassy A to Z ratios of at least 37:63, higher ratios are also ofadvantage such as 38:62, 39:61, 40:60, 41:59, 42:58, 43:57, 44:65,45:55, 46:54, 47:53, 48:52, 49:51, 50:50, 51:49, 52:48, 53:47, 54:46,55:45, 56:44, 57:43, 58:42, 59:41, 60:40, 61:39, 62:38, 63:37, 64:36,65:35, 66:34, while lower ratios may also be of advantage (but less so)such as 35:65 and 36:64; or by the addition of

[0091] (d) sufficient amounts of glassy homopolymers or glass associatedphase resins so that condition (c) is met

[0092] It is believed that the combination of sufficient amounts ofcrystallinity and sufficient amounts glassy A components of thecopolymers in combination with low viscosity plasticizers impartsnon-tackiness to the gels of the invention. It is therefore contemplatedthat the same effect can be achieved by blending highly crystalline andhighly glassy copolymers (Dow S, M, & E Series E-S-E), with lesscrystalline and less glassy copolymers such as amorphous SEPS, SEBS, andamorphous S-EB-EP-S and other amorphous copolymers provided theamorphous copolymers are in minor amounts and there is substantialcrystallinity and sufficient over all glassy A components to meetconditions (c).

[0093] The glassy homopolymers of (d) are advantageously selected fromone or more homopolymers of polystyrene, poly(alpha-methylstyrene),poly(o-methylstyrene), poly(m-methylstryene), poly(p-methylstyrene), andpoly(dimethylphenylene oxide) The average molecular weight of the glassyhomopolymers advantageously can range from about 2,500 to about 90,000,typical about 3,000; 4,000; 5,000; 6,000; 7,000; 8,000; 9,000; 10,000;11,000; 12,000, 13,000; 14,000; 15,000; 16,000, 17,000; 18,000; 19,000;20,000; 30,000; 40,000; 50,000; 60,000; 70,000; 80,000; 90,000 and thelike. Example of various molecular weights of commercially availablepolystyrene: Aldrich Nos.: 32,771-9 (2,500M_(w)), 32,772-7 (4,000 Mw),37,951-4 (13,000 Mw), 32-774-3 (20,000 Mw), 32,775-1 (35,000 Mw),33,034-5 (50,000 Mw), 32,778-8 (90,000 Mw); poly(alpha-methylstyrene)#41,794-7 (1,300 Mw), 19,184-1 (4,000 Mw); poly(4-methylstyrene)#18,227-3 (72,000 Mw), Endex 155, 160, Kristalex 120, 140 from HerculesChemical, GE: polyphenylene ether. Blendex 820, HPP825, HPP830, HPP857,HPP820, HPP822, HPP823, and the like. Various glassy phase associatingresins having softening points above about 120° C. can also serve toincrease the glassy phase of the Gels of the invention and met thenon-tackiness critena, these include: Hydrogenated aromatic resins(Regalrez 1126, 1128, 1139, 3102, 5095, and 6108), hydrogenated mixedaromatic resins (Regalite R125), and other aromatic resin (Picco 5130,5140, 9140, Cumar LX509, Cumar 130, Lx-1035) and the like.

[0094] On the other hand, the molten gelatinous elastomer compositionwill adhere sufficiently to certain plastics (e.g. acrylic, ethylenecopolymers, nylon, polybutylene, polycarbonate, polystyrene, polyester,polyethylene, polypropylene, styrene copolymers, and the like) providedthe temperature of the molten gelatinous elastomer composition issufficient high to fuse or nearly fuse with the plastic. In order toobtain sufficient adhesion to glass, ceramics, or certain metals,sufficient temperature is also required (e.g. above 250° F.). Commercialresins which can aid in adhesion to materials (plastics, glass, andmetals) may be added in minor amounts to the gelatinous elastomercomposition, these resins include: Super Sta-tac, Nevtac, Piccotac,Escorez, Wingtack, Hercotac, Betaprene, Zonarez, Nirez, Piccolyte,Sylvatac, Foral, Pentalyn, Arkon P, Regalrez, Cumar LX, Picco 6000,Nevchem, Piccotex, Kristalex, Piccolastic, LX-1035, and the like

[0095] The commercial resins which can aid in adhesion to materials(plastics, glass, and metals) may be added in minor amounts to thegelatinous elastomer composition, these resins include: polymerizedmixed olefins (Super Sta-tac, Betaprene Nevtac, Escorez, Hercotac,Wingtack, Piccotac), polyterpene (Zonarez, Nirez, Piccolyte, Sylvatac),glycerol ester of rosin (Foral), pentaerythritol ester of rosin(Pentalyn), saturated alicyclic hydrocarbon (Arkon P), coumarone indene(Cumar LX), hydrocarbon (Picco 6000, Regalrez), mixed olefin (Wingtack),alkylated aromatic hydrocarbon (Nevchem), Polyalphamethylstyrene/vinyltoluene copolymer (Piccotex), polystyrene (Kristalex, Piccolastic),special resin (LX-1035), and the like. More earlier, I had alsodisclosed the use of liquid tackifiers in high viscosity SEBS gels.

[0096] The incorporation of such adhesion resins is to provide strongand dimensional stable adherent gels, gel composites, and gel articles.Typically such adherent gels can be characterized as adhesive gels, softadhesives or adhesive sealants. Strong and tear resistant adherent gelsmay be formed with various combinations of substrates or adhere (attach,cling, fasten, hold, stick) to substrates to form adherent gel/substratearticles and composites.

[0097] GE polyphenylene ether can be added in minor amounts to the gelto improve crack or craze resistance when the gel is under stress orshear conditions. The amount can vary from less than about 1 part byweight of copolymer to about 15 parts by weight of copolymer. Suchamounts include 00.1, 00.2, 00.5, 00.8, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6,0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,17, 18, 19, 20 parts by weight of copolymer(s).

[0098] Various substrate and adherent gel combinations (FIGS. 1-4 x.)which can be utilized to form composite adherent gel articles include:G_(n)M_(n), G_(n)G_(n), G_(n)M_(n)G_(n), M_(n)G_(n)M_(n),M_(n)G_(n)G_(n), G_(n)G_(n)M_(n), G_(n)G_(n)M_(n), G_(n)M_(n)M_(n)G_(n),M_(n)G_(n)G_(n)M_(n), M_(n)M_(n)G_(n)G_(n), M_(n)M_(n)M_(n)G_(n)G_(n),G_(n)M_(n)G_(n)G_(n), G_(n)M_(n)G_(n)M_(n)M_(n),M_(n)G_(n)M_(n)G_(n)M_(n)G_(n)M_(n), or any permutations of saidcombination, where G=gel and M=material. The subscript 1, 2, 3, 4, etc.,are different and is represented by n which is a positive number, when nis a subscript of M, n may be the same or different material and when nis a subscript of G, n can be the same or different rigidity adherentgel or the same or different adherent gel material composition. Thematerial (M) suitable for forming composite articles with the gelatinouselastomer compositions can include foam, plastic, fabric, metal,concrete, wood, wire screen, refractory material, glass, syntheticresin, synthetic fibers, and the like. Sandwiches of adherentgel/material (i e adherent gel-material-adherent gel ormaterial-adherent gel-material, etc.) are ideal for use as shockabsorbers, acoustical isolators, vibration dampers, vibration isolators,and wrappers. For example the vibration isolators can be use underresearch microscopes, office equipment, tables, and the like to removebackground vibrations.

[0099] Various useful adhesion resins of one or more types can beincorporated in minor amounts into the adherent gel. These include:polymerized mixed olefins, polyterpene, glycerol ester of rosin,pentaerythritol ester of rosin, saturated alicyclic hydrocarbon,coumarone indene, hydrocarbon, mixed olefin, alkylated aromatichydrocarbon, Polyalphamethylstyrene/vinyl toluene copolymer,polystyrene, special resin, and the like.

[0100] The adherent gel compositions of the invention can be casted untovarious substrates, such as foam, plastic, fabric, metal, concrete,wood, wire screen, refractory material, glass, synthetic resin,synthetic fibers, and the like, or the adherent gels formed and then canbe adhere (attach, cling, fasten, hold, stick) to the desired substratesto form various GnMn, GnGn, GnMnGn, MnGnMn, MnGnGn, GnGnMn, GnGnMn,GnMnMnGn, MnGnGnMn, MnMnGnGn, MnMnMnGnGn, GnMnGnGn, GnMnGnMnMn,MnGnMnGnMnGnMn, or any permutations of said combination composites foruses requiring temporary peel and re-use as well as permanent long-lifeuse as needed. Adhesion to substrates is most desirable when it isnecessary to apply the adherent gels to substrates in the absence ofheat or on to a low temperature melting point substrate for later peeloff after use, such as for sound damping of a adherent gel compositeapplied to a first surface and later removed for use on a secondsurface. The low melting substrate materials which can not be exposed tothe high heat of the molten adherent gels, such as low melting metals,low melting plastics (polyethylene, PVC, PVE, PVA, and the like) canonly be formed by applying the adherent gels to the temperaturesensitive substrates. Other low melting plastics include. polyolefinssuch as polyethylene, polyethylene copolymers, ethylene alpha-olefinresin, ultra low density ethylene-octene-1 copolymers, copolymers ofethylene and hexene, polypropylene, and etc. Other cold applied adherentgels to teflon type polymers: TFE, PTFE, PEA, FEP, etc, polysiloxane assubstrates are achieved using the adherent gels of the invention.

[0101] Likewise, adherent gel substrate composites can be both formed bycasting hot onto a substrate and then after cooling adhering theopposite side of the adherent gel to a substrate having a low meltingpoint. The adherent gel is most essential when it is not possible tointroduce heat in an heat sensitive or explosive environment or in outerspace. The use of solid or liquid resins promotes adherent gel adhesionto various substrates both while the adherent gel is applied hot or atroom temperature or below or even under water. The adherent gels can beapplied without heating to paper, foam, plastic, fabric, metal,concrete, wood, wire screen, refractory material, glass, syntheticresin, synthetic fibers, and the like.

[0102] The adhesion properties of the gels are determined by measuringcomparable rolling ball tack distance “D” in cm using a standarddiameter “d” in mm stainless steel ball rolling off an inclined ofheight “H” in cm and determining the average force required to perform180° peel of a heat formed G₁M₁ one inch width sample applied at roomtemperature to a substrate M₂ to form the composite M₁G₁M₂ The peel at aselected standard rate cross-head separation speed of 25 cm/minute atroom temperature is initiated at the G₁M₂ interface of the M₁G₁M₂composite, where the substrate M₂ can be any of the substrates mentionedand M₁ preferably a flexible fabric.

[0103] Advantageously, glassy phase associating homopolymers such aspolystyrene and aromatic resins having low molecular weights of fromabout 2,500 to about 90,000 can be blended with the triblock copolymersof the invention in large amounts with or without the addition ofplasticizer to provide a copolymer-resin alloy of high impact strengths.More advantageously, when blended with multiblock copolymers andsubstantially random copolymers the impact strengths can be even higher.The impact strength of blends of from about 150 to about 1,500 parts byweight glass phase associating polymer and resins to 100 parts by weightof one or more multiblock copolymers can provide impact strengthapproaching those of soft metals. At the higher loadings, the impactstrength approaches that of polycarbonates of about 12 ft-lb/in notchand higher.

[0104] The improvements of the gels of the invention is exceptional, thegels are crystal to the touch and can be quantified using a simple testby taking a freshly cut Gel probe of a selected gel rigidity made fromthe gels of the invention. The gel probe is a substantially uniformcylindrical shape of length “L” of at least about 3.0 cm formedcomponents (1)-(3) of the gels of the invention in a 16×150 mm testtube. The gel probe so formed has a 16 mm diameter hemi-spherical tipwhich (not unlike the shape of a human finger tip) is brought intoperpendicular contact about substantially the center of the top cover ofa new, untouched polystyrene reference surface (for example the topcover surface of a sterile polystyrene petri dish) having a diameter of100 mm and a weight of 7.6 gram resting on its thin circular edge (whichminimizes the vacuum or partial pressure effects of one flat surface incontact with another flat surface) on the flat surface of a scale whichscale is tared to zero. The probe's hemi-spherical tip is place incontact with the center of the top of the petri dish cover surface andallowed to remain in contact by the weight of the gel probe while heldin the upright position and then lifted up. Observation is maderegarding the probe's tackiness with respect to the clean referencepolystyrene surface. For purpose of the foregoing reference tack test,tackiness level 0 means the polystyrene dish cover is not lifted fromthe scale by the probe and the scale shows substantially an equalpositive weight and negative weight swings before settling again back tozero with the swing indicated in (negative) grams being less than 1.0gram. A tackiness level of one 1, means a negative swing of greater than1.0 gram but less than 2.0 gram, tackiness level 2, means a negativeswing of greater than 2 gram but less than 3 gram, tackiness level 3,means a negative swing of greater than 3 gram but less than 4 gram,before settling back to the zero tared position or reading Likewise,when the negative weight swing of the scale is greater than the weightof the dish (i.e., for the example referred above, greater than 7.6gram), then the scale should correctly read −7.6 gram which indicatesthe dish has completely been lifted off the surface of the scale. Suchan event would demonstrate the tackiness of a gel probe havingsufficient tack on the probe surface. The gels of the invention fails tolift off the polystyrene reference from the surface of the scale whensubject to the foregoing reference tack test. Advantageously, the gelsof the invention can register a tackiness level of less than 5, moreadvantageously, less than 3, still more advantageously, less than 2, andstill more advantageously less than 1. The non-tackiness of the gels ofthe invention can advantageously range from less than 6 to less than 0.5grams, typical tack levels are less than 0.2, 0.3, 0.4, 0.5, 0.6, 0.7,0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1,2.2, 2.3, 2.5, 2.8, 3.0, 3.5, 4.0, 4.5, 5.0 grams and the like. Whereasprobes of gels made from amorphous gels such as SEPS, SEBS, S-EP-EB-S,and the like with copolymer styrene to rubber ratio of less than 37:63and plasticizer of higher than 30 cSt 40° C. are found to lift thepolystyrene reference from the surface of the scale. For purposes ofindicating tack, the method above can provide gel tack level readings of1, 2, 3, 4, 5, 6, and 7 grams. More accurate and sensitive readings canbe made using electronic scales of tack levels of less than 1 gram. Bythis simple method tack levels (of a gel probe on a polystyrenereference surface) can be measure in terms of gram weight displacementof a scale initially tared to zero. For purpose of the present inventionthe method of using a polystyrene reference surface having a weight of7.6 grams in contact and being lifted by the tackiness of a cylindricalgel probe having a 16 mm diameter hemi-spherical tip is used todetermine the tackiness of the gels of the invention. The level of tackbeing measured in gram Tack at 23° C.

[0105] The improvements of other properties of the gels over amorphousgels are many, these include: improved damage tolerance, improved crackpropagation resistance, improved tear resistance, improved resistance tofatigue, etc Such gels are advantageous for end-use involving repeatedapplications of stress and strain resulting from large number of cyclesof deformations, including compression, compression-extension(elongation), torsion, torsion-compression, torsion-elongation, tension,tension-compression, tension-torsion, etc. The gels also exhibitimproved damage tolerance, crack propagation resistance and especiallyimproved resistance to high stress rupture which combination ofproperties makes the gels advantageously and surprisingly exceptionallymore suitable than amorphous gels made from non-poly(ethylene) componentcopolymers at corresponding gel rigidities.

[0106] Block copolymers with polyethylene midblocks alone do not formsuitable Gels for purpose of the invention. Polyethylene midblockregions needs to be balanced with amorphous midblock regions in order toobtain soft, flexible and elastic gels with the desired tear resistantproperties that are not found in totally amorphous gels.

[0107] The various representative polyethylene/glassy domain/amorphousstructures of S-E-EB-S, S-E-EB₂₅-S, S-E-EP-E-S, S-EP-E-S andS-EP-E-EP-S. Although the structure are spheroid representation,cylinders and plates are also within the scope of the present invention.Cylinder and plate structure are obtained with increasing glassy A endblocks. From about 15-30% by weight of A blocks, the block copolymerstructure is spheroid. From about 33 about 40% by weight of A blocks,the block copolymer structure becomes cylindrical; and above about 45% Ablocks, the structure becomes less cylindrical and more plate like.

[0108] Generally, one or more (E) midblocks can be incorporated atvarious positions along the midblocks of the block copolymers. Using thesequential process for block copolymer synthesis, The (E) midblocks canbe positioned as follows: a) A-E-W-A b) A-E-W-E-A c) A-W-E-W-A d)A-E-W-E-W-E-W-E-A e) A-W-E-W-A-E-A-E-W-E-A f) and etc.

[0109] The lower flexibility of block copolymer gels due to (E)midblocks can be balanced by the addition of sequentially (W) midblocks.For example, the sequentially synthesized block copolymer SE-EB-S canmaintain a high degree of flexibility due to the presence of amorphous-EB- block. The sequential block copolymer S-E-EB-B-S can maintain ahigh degree of flexibility due to the presence of amorphous -EB- and -B-midblocks. The sequential block copolymer S-E-EP-E-S can maintain a highdegree of flexibility due to the presence of -EP- midblock Thesequential block copolymer S-E-B-S can maintain a high degree offlexibility due to the presence of the -B- midblock. For S-E-S, wherethe midblock is substantially crystalline and flexibility low, physicalblending with amorphous block copolymers such as S-EB-S, S-B-S, S-EP-S,S-EB-EP-S, (S-EP)n and the like can produce more softer, less rigid, andmore flexible gel.

[0110] Because of the (E) midblocks, the gels of the invention exhibitdifferent physical characteristics and improvements over substantiallyamorphous gels including damage tolerance, improved crack propagationresistance, improved tear resistance producing knotty tears as opposedto smooth tears, crystalline melting point of at least 28° C., improvedresistance to fatigue, higher hysteresis, etc. Moreover, the gels whenstretched exhibit additional yielding as shown by necking caused bystress induced crystallinity. Additionally, the crystallization rates ofthe crystalline midblocks can be controlled and slowed depending onthermal history producing time delay recovery upon deformation.

[0111] Regarding resistance to fatigue, fatigue (as used herein) is thedecay of mechanical properties after repeated application of stress andstrain. Fatigue tests give information about the ability of a materialto resist the development of cracks or crazes resulting from a largenumber of deformation cycles. Fatigue test can be conducted bysubjecting samples of amorphous and gels to deformation cycles tofailure (appearance of cracks, crazes, rips or tears in the gels).

[0112] The invention gels can be made to exhibit sufficient low GramTack to be noticeable non-tacky to the touch of the fingers of a typicalhuman hand at 23° C. A simple way to accurately measure the non tackyfeeling as sensed by the fingers is to drop a reference gel samplehaving a cylindrical shape of about 1.0 cm diameter and 1.0 cm in lengtha distance of 10 cm on to the surface of a polystyrene petri dish havinga diameter of 10 cm inclined at 45°. The reference gel sample isconsidered non tacky if it (1) “bounce at least twice before coming torest”, (2) “bounce off”, (3) “bounce and then rolls off”, or (4) “rollsoff” on striking the polystyrene surface. If none of (1) thru (4) isobserved, then the level of Gram Tack can be determined by the gelsample method above.

[0113] The invention gel composition comprises at least one highviscosity linear multiblock copolymers and star-shaped (or radial)multiblock copolymers The invention gel compositions copolymer (I)comprises 100 parts by weight of one or a mixture of two or more of ahydrogenated styrene isoprene/butadiene block copolymer(s) morespecifically, hydrogenated styrene block polymer with2-methyl-1,3-butadiene and 1,3-butadiene) orpoly(styrene-ethylene-ethylene-propylene-styrene) SEEPS orpoly(styrene-ethylene-ethylene-propylene)_(n), (SEEP)_(n).

[0114] In general such block copolymers have the general configurationsA^(n)-Z-A^(n) and (A^(n)-Z)_(n) wherein each A^(n) is a selected glassypolymer end block of a monoalkenyl arene compounds, more specifically, amonovinyl aromatic compounds such as polystyrene (where superscriptn=1), monovinylnaphithalene as well as the alkylated derivatives thereofsuch as poly(alpha-methylstyrene) (n=2), poly(o-methylstyrene) (n=3),poly(m-methylstryene) (n=4), poly(p-methylstyrene) (n=5)poly(tertiary-butylstyrene) (n=6), and the like, and midblocks (Z)comprising polymer chains of poly(ethylene), poly(ethylene) andpoly(propylene) or -EEP-. In the case of styrene glassy end blocks, thehydrogenated styrene isoprene/butadiene block copolymer(s) have theformula

[0115] The SEEPS (I) linear copolymers are characterized as having aBrookfield Viscosity value at 5 weight percent solids solution intoluene at 30° C. of from less than about 40 cps to about 150 cps andhigher, advantageously from about 40 cps to about 60 cps and higher,more advantageously from about 50 cps to about 80 cps and higher, stillmore advantageously from about 70 cps to about 110 cps and higher, andeven more advantageously from about 90 cps to about 180 cps and higher.

[0116] The (I) star-shaped copolymers are characterized as having aBrookfield Viscosity value at 5 weight percent solids solution intoluene at 30° C. of from about 150 cps to about 380 cps and higher,advantageously from about 150 cps to about 260 cps and higher, moreadvantageously from about 200 cps to about 580 cps and higher, and stillmore advantageously from about 500 cps to about 1,000 cps and higher.

[0117] This physical elastomeric network structure of the invention gelsare reversible, and heating the polymer above the softening point of theglassy domains temporarily disrupt the structure, which can be restoredby lowering the temperature. During mixing and heating in the presenceof compatible plasticizers, the glassy domains (A) unlock due to bothheating and solvation and the molecules are free to move when shear isapplied. The disruption and ordering of the glassy domains can be viewedas a unlocking and locking of the elastomeric network structure. Atequilibrium, the domain structure or morphology as a function of the (A)and (Z) phases (mesophases) can take the form of spheres, cylinders,lamellac, or bicontinous structures. The scale of separation of thephases are typically of the order of hundreds of angstroms, dependingupon molecular weights (i.e Radii of gyration) of the minority-componentsegments. The sub-micron glassy domains which provides the physicalinterlocking are too small to see with the human eye, too small to seeusing the highest power optical microscope and only adequately enough tosee using the electron microscope. At such small domain scales, when thegel is in the molten state while heated and brought into contact to beformed with any substrate and allowed to cool, the glassy domains of thegel become interlocked with the surface of the substrate. Atsufficiently high enough temperatures, with or without the aid of otherglassy resins (such as polystyrene homopolymers and, the like), theglassy domains of the copolymers forming the invention gels fusses andinterlocks with even a visibly smooth substrate surface such as glass.The disruption of the sub-micron domains due to heating above thesoftening point forces the glassy domains to open up, unlocking thenetwork structure and flow. Upon cooling below the softening point theglassy polymers reforms together into sub-micron domains, locking into anetwork structure once again, resisting flow. It is this unlocking andlocking of the network structure on the sub-micron scale with thesurfaces of various materials which allows the gel to form interlockingcomposites with other materials.

[0118] A useful analogy is to consider the melting and freezing of awater saturated substrate, for example, foam, cloth, fabric, paper,fibers, plastic, concrete, and the like. When the water is frozen, theice is to a great extent interlocked with the substrate and upon heatingthe water is able to flow. Furthermore, the interlocking of the ice withthe various substrates on close examination involves interconnecting icein, around, and about the substrates thereby interlocking the ice withthe substrates. A further analogy, but still useful is a plant or weedwell established in soil, the fine roots of the plant spreads out andinterconnects and forms a physical interlocking of the soil with theplant roots which in many instances is not possible to pull out theplant or weed from the ground without removing the surrounding soilalso.

[0119] Likewise, because the glassy domains are typically about 200Angstroms in diameter, the physical interlocking involve domains smallenough to fit into and lock with the smallest surface irregularities, aswell as, flow into and flow through the smallest size openings of aporous substrate. Once the gel comes into contacts with the surfaceirregularities or penetrates the substrate and solidifies, it becomesdifficult or impossible to separate it from the substrate because of thephysical interlocking. When pulling the gel off a substrate, most oftenthe physically interlocked gel remains on the substrate. Even a surfacewhich may appear perfectly smooth to the eye, it is often not the caseExamination by microscopy, especially electron microscopy, will showserious irregularities. Such irregularities can be the source ofphysical interlocking with the gel.

[0120] The polyethylene midblock containing block copolymers of theinvention gel are the result of hydrogenation of butadiene. In order forthe block copolymers forming the invention gel to exhibit polyethylenecrystallinity, the midblock segments must contain long runs of —CH₂—groups. There should be approximately at least 16 units of —(CH₂)— insequence for crystallinity. Only the (—CH₂—)⁴ units can crystallize, andthen only if there are at least 4 units of (—CH₂—)4 in sequence;alternatively, the polyethylene units are denoted by[—(CH₂—CH₂—CH₂—CH₂)—]⁴, [(—CH₂—)⁴]⁴ or (—CH₂—)¹⁶.

[0121] The polyethylene crystalline segments or midblocks of copolymersforming the invention gel can be characterized by the presence of amelting trace of from less than about 2.5° C. (for low viscositypolyethylene midblock containing block copolymers) to greater than about18° C. (for higher viscosity polyethylene midblock containing blockcopolymers) as determined by crystallization exotherm DSC curve. Morespecific DSC melting values of the crystalline midblock block segment ofthe SEEPS copolymers may be carefully measured and detected include lessthan about 1.5° C., 2° C., 3° C., 4° C., 5° C., 6° C., 7° C., 8° C., 9°C., 10° C., 11° C., 12° C., 13° C., 14° C., 15° C., 16° C., 17° C., 18°C., 19° C., 20° C., 21° C., 22° C., 23° C., 24° C., 25° C., 26° C., 27°C., 28° C., 29° C., 30° C., 31° C., 32° C., 33° C., 34° C., 35° C., 36°C., 37° C., 38° C., 39° C., 40° C., 41° C., 42° C., 43° C., 44° C., 45°C., 46° C., 47° C., 48° C., 49° C., 50° C., 51° C., 52° C., 53° C., 54°C., 55° C., and higher. Whereas, the melting trace in DSC evidencing thepresence of crystalline polyethylene are not found in amorphous blockcopolymers such as SEPS.

[0122] The crystallization exotherm of the crystalline block copolymerinvention gel are determined by ASTM D 3417 method. In order to provideconditions for DSC samples of certain polyethylene midblock containingblock copolymers to have the best possible chance to exhibit anycrystallinity the measurement protocol can be modified as follows: heatto 140° C. @ 10° C./min., cool to 0° C. @ 2° C./min, put sample infreezer for 1 week, heat sample to 140° C. @ 1° C./min, then cool to 0°C./min

[0123] Generally, the method of obtaining long runs of crystalline—(CH₂)— is by sequential block copolymer synthesis followed byhydrogenation. The attainment of invention gels is solely due to theselective polymerization of the butadiene monomer (forming themidblocks) resulting in one or more predetermined amount of 1,4poly(butadiene) blocks followed by sequential polymerization ofadditional midblocks and hydrogenation to produce one or morecrystalline midblocks of the final block copolymers.

[0124] The crystalline block copolymers are made by sequential blockcopolymer synthesis, the percentage of crystallinity or (—CH₂—)¹⁶ unitsshould be at least about (0.67)⁴ or about 20% and actual crystallinityof about 12%. For example, a selective synthesized S-EBn-S copolymerhaving a ratio of 33:67 of 1,2 and 1,4 poly(butadiene) on hydrogenationwill result in a midblock with a crystallinity of (0.67)⁴ or 20%. Forsake of simplicity, when n is a subscript of -EB-, n denotes thepercentage of (—CH₂—)⁴ units, eg, n=33 or 20% crystallinity which is thepercentage of (0.67)⁴ or “(—CH₂—)¹⁶” units. Thus, when n=28 or 72% of(—CH₂—)⁴ units, the % crystallinity is (0.72)⁴ or 26.87% crystallinityattributed to (—CH₂—)¹⁶ units, denoted by -EB₂₈-. As a matter ofconvention, and for purposes of this specification involvinghydrogenated polybutadiene: the notation -E- denotes at least about 85%of (—CH₂—)⁴ units. The notation -B- denotes at least about 70% of[—CH₂—CH(C₂H₅)—] units. The notation -EB- denotes between about 15 and70% [—CH₂—CH(C₂H₅)—] units. The notation -EBn- denotes n%[—CH₂—CH(C₂H₅)—] units, For hydrogenated polyisoprene. The notation -EP-denotes about at least 90% [—CH₂—CH(CH₃)—CH₂—CH₂—] units.

[0125] Generally, one or more (E) midblocks can be incorporated atvarious positions along the midblocks of the block copolymers. The lowerflexibility of block copolymer gels due to (E) midblocks can be balancedby the addition of sequentially (W) midblocks. For example, thesequentially synthesized block copolymer S-E-EB-S can maintain a highdegree of flexibility due to the presence of amorphous -EB- block. Thesequential block copolymer S-E-EB-B-S can maintain a high degree offlexibility due to the presence of amorphous -EB- and -B- midblocks. Thesequential block copolymer S-E-EP-E-S can maintain a high degree offlexibility due to the presence of -EP- midblock. The sequential blockcopolymer S-E-B-S can maintain a high degree of flexibility due to thepresence of the -B- midblock. For S-E-S, where the midblock may becrystalline and flexibility low, physical blending with amorphous blockcopolymers such as S-EP-S, S-EB-EP-S, (S-EP)_(n) and the like canproduce more softer, less rigid, and more flexible gel.

[0126] Because of the high viscosity of the block copolymers and (E)midblocks, the invention gel exhibit different physical characteristicsand improvements over amorphous gels including damage tolerance,improved crack propagation resistance, improved tear resistanceproducing knotty tears as opposed to smooth tears, improved resistanceto fatigue, higher hysteresis, etc. Moreover, the invention gels whenstretched exhibit additional yielding as shown by necking caused bystress induced crystallinity or yielding of the styrene glassy phases.

[0127] Regarding resistance to fatigue, fatigue (as used herein) is thedecay of mechanical properties after repeated application of stress andstrain. Fatigue tests give information about the ability of a materialto resist the development of cracks or crazes resulting from a largenumber of deformation cycles. Fatigue test can be conducted bysubjecting samples of amorphous and gels to deformation cycles tofailure (appearance of cracks, crazes, rips or tears in the gels).

[0128] Tensile strength can be determined by extending a selected gelsample to break as measured at 180° U bend around a 5.0 mm mandrelattached to a spring scale. Likewise, tear strength of a notched samplecan be determined by propagating a tear as measured at 180° U bendaround a 5.0 mm diameter mandrel attached to a spring scale.

[0129] Various block copolymers can be obtained which are amorphous,highly rubbery, and exhibiting minimum dynamic hysteresis.

Block Copolymer S-EB-S

[0130] The monomer butadiene can be polymerized in a ether/hydrocarbonsolvent to give a 50/50 ratio of 1,2 poly(butadiene)/1,4 poly(butadiene)and on hydrogenation no long runs of —CH₂— groups and negligiblecrystallinity, ie, about (0.5)⁴ or 0.06 or 6% and actual crystallinityof about 3%. Due to the constraints of Tg and minimum hysteresis,conventional S-EB-S have ethylene-butylene ratios of about 60:40 with acrystallinity of about (0.6)⁴ or 0.129 or 12% and actual crystallinityof about 7.7%.

Block Copolymer S-EP-S

[0131] The monomer isoprene when polymerized will produce 95% 1,4poly(isoprene)/5% 3,4 poly(isoprene) and upon hydrogenation will formamorphous, rubbery poly(ethylene-propylene) midblock and no long runs of—CH₂— and no crystallinity.

Mixed Block Copolymer S-EB/EP-S

[0132] The polymerization of a 50/50 mixture of isoprene/butadienemonomers in suitable ether/hydrocarbon solvents to give equal amounts of1,2 and 1,4 poly(butadiene) on hydrogenation will produce a maximumcrystallinity of (0.25)⁴ or 0.4%. The actual crystallinity would beapproximately about 0.2%, which is negligible and results in a goodrubbery midblock.

[0133] The polymerization of a 80/20 mixture of isoprene/butadienemonomers in suitable ether/hydrocarbon solvents to give equal amounts of1,2 and 1,4 poly(butadiene) will upon hydrogenation produce a lowcrystallinity of (0.10)⁴ or 0.01%. The actual crystallinity would beapproximately about 0.006%, which is negligible and results in a goodrubbery midblock.

[0134] The polymerization of a 20/80 mixture of isoprene/butadienemonomers in suitable ether/hydrocarbon solvents to give equal amounts of1,2 and 1,4 poly(butadiene) will upon hydrogenation produce a lowcrystallinity of (0.4)⁴ or 2.56%. The actual crystallinity would beapproximately about 1.53%, which is negligible and results in a goodrubbery midblock.

Block Copolymer S-EEP-S

[0135] The polymerization of a 20/80 mixture of isoprene/butadienemonomers in suitable ether/hydrocarbon solvents to give a 40:60 ratio of1,2 and 1,4 poly(butadiene) will upon hydrogenation produce a lowcrystallinity of (0.48)⁴ or 5.3%. The actual crystallinity would beapproximately about 3.2%, which is negligible and results in a goodrubbery midblock. This theoretical % of actual crystallinity correspondswell to commercially available SEEPS Septon 4033 and 4055 which varieswith batch lots.

[0136] For purpose of convince and simplicity, the hydrogenatedpolybutadiene are denoted as follows: -E- denotes at least 85% R-1units, -B- denotes at least 70% R-2 units, -EB- denotes between 15 and70% R-2 units, -EBn- denotes n% R-2 units, and -EP- denotes 90% R-3units.

[0137] Table I below gives the % of units on hydrogenation ofpolybutadiene/polyisoprene copolymer midblocks

|H2

[0138]

[0139] n% from polybutadiene (1-n)% from polyisoprene

[0140] 90%·n 10%·n 95%·(1-n) 5%·(1-n)

[0141] where n is the mole % polybutadiene in thepolybutadiene-polyisoprene starting polymer n = R-1 R-2 R-3 R-4  0%  0%0% 95% 5% 20% 18% 2% 76% 4% 40% 36% 4% 57% 3% 60% 54% 6% 38% 2% 80% 72%8% 19% 1% 100%  90% 10%   0% 0%

[0142] where R-1 denotes (—CH₂—)⁴,

[0143] R-2 denotes —(CH—CH₂)—,

C₂H₅

[0144] R-3 denotes —(CH₂—CH—CH₂—CH₂)—, and

CH₃

[0145] R4 denotes —(CH₂—CH)—

CH

CH₃CH₃

[0146] Therefore, the percentage that can crystallize is [(—CH₂—)⁴]⁴since this is the chance of getting four (—CH₂—)⁴ units in sequence. Thepercentage that will crystallize is about 60% of this. n = (—CH₂—)⁴[(—CH₂—)⁴]⁴ 0.6 × [(—CH₂—)⁴]_(n)  0%  0%   0%   0% 20% 18%  0.1% 0.06%40% 36%  1.7%  1.0% 60% 54%  8.5%  5.1% 80% 72% 26.9% 16.1% 100%  90%65.6% 39.4%

[0147] This applies to polymerization in a hydrocarbon solvent. In anether (eg, diethylether), the percentage (—CH₂—)⁴ units will be reducedso that crystallinity will be negligible. n = (—CH₂—)⁴ [(—CH₂—)⁴]⁴ 0.6 ×[(—CH₂—)⁴]^(n)  0%  0%   0%   0% 20%  5% 0.0006%  0.0004%  40% 10% 0.01%0.006%  60% 15% 0.05% 0.03% 80% 20% 0.16% 0.10% 100%  25% 0.39% 0.23%

[0148] These values are all negligible. There will be no detectablecrystallinity in any of these polymer midblocks. In a mixedether/hydrocarbon solvent, values will be intermediate, depending on theratio of ether to hydrocarbon.

[0149] The midblock components (Z) can comprise various combinations ofmidblocks between the selected end blocks (A); these include: -E-EB-,-E-EP-, -E-EP-E-, -E-EB-E-, -E-E-EP-, -E-E-EB-, and the like.

[0150] The (Z) midblock of two or more polymer chains can be obtained byhydrogenation methods, for example: 1,4-polybutadiene (B_(1,4)) can beconverted by hydrogenation to poly(ethylene), 1,4-polybutadiene(B_(1,4)) and 1,2-polybutadiene (B_(1,2)) can be converted byhydrogenation to poly(ethylene-butylene), 1,4-poly-isoprene (I_(1,4))can be converted by hydrogenation to poly(ethylene-propylene),1,2-polybutadiene (B_(1,2)) can be converted by hydrogenation to atacticpoly(1-butene)(polybutylene), 1,4-polybutadiene (B_(1,4)) andpolyisoprene (I) 1,4-poly-butadiene (B_(1,4)) can be converted byhydrogenation to poly(ethylene-ethylene-co-propylene-ethylene),2-methyl-1,3-polybutadiene and 1,3-polybutadiene (I, B_(1,3)) can beconverted by hydrogenation to poly(ethylene-ethylene-co-propylene), andthe like. Polypropylene can be modified by tailblocking apoly(ethylene-propylene) copolymer segment on the propylene block toform poly(propylene-ethylene-co-propylene); likewise,poly(ethylene-propylene)_(n) (EP),poly(propylene-ethylene-co-propylene-propylene) (P-EP-P),poly(propylene-ethylene-propylene) (P-E-P),poly(ethylene-ethylene-copropylene) (E-EP) can be formed. It is notedherein that B (bold) denotes polybutadiene and B (plain) denotespolybutylene.

[0151] Further, the multiblock copolymers (A^(n)-Z-A^(n)) can beobtained by various synthesis methods including hydrogenation ofselected block copolymers. When the subscript n of A is=1, (polystyrene)(S), for example, suitable block copolymers can be converted to theuseful multiblock copolymers forming the invention gels. These include:conversions of S-I-B_(1,3)-S to (S-E-EP-S), S-B_(1,4)-I-B_(1,4)-S to(S-E-EP-E-S), S-B_(1,2)-I-S to (S-B-EP-S), S-B_(1,3)-B_(1,2)-B_(1,4)-Sto (S-E-EB-S), S-B_(1,4)-B_(1,2)-I-S to (S-EB-EP-S),S-I-B_(1,3)-B_(1,2)-B_(1,4)-S to (S-E-EP-EB-S), etc. As denoted hereinabbreviations are interchangeably used, for example, (S-E-EP-S) denotespoly(styrene-ethylene-ethylene-co-propylene-styrene). Other linearmultiblock copolymers (denoted in abbreviations) can be formed,including: (S-B-EB-S), (S-E-EB-E-S), (S-B-EP-E-S), (S-B-EB-E-S),(S-E-E-EP-S), (S-E-E-EB-S), and the like.

[0152] The multiblock star-shaped (or radial) copolymers (A^(n)-Z)_(n)can be obtained by various synthesis methods including hydrogenation ofselected block copolymers. When the subscript n of A is=1, (polystyrene)(S), for example, suitable block copolymers can be converted to theuseful multiblock copolymers forming the invention gels. These include:conversions of (S-I-B_(1,3))_(n) topoly(styrene-ethylene-ethylene-co-propylene)_(n) denoted by theabbreviation (S-E-EP)_(n), (S-B_(1,4)-I-B_(1,4))_(n) to (S-E-EP-E)_(n),S-B_(1,2)-I)_(n) to (S-B-EP)_(n), (S-B_(1,3)-B_(1,2)-B_(1,4))_(n) to(S-E-EB)_(n), (S-B_(1,4)-B_(1,2)-I)_(n) to (S-EB-EP)_(n),(S-I-B_(1,3)-B_(1,2)B_(1,4))_(n) to (S-E-EP-EB)_(n), etc. Othermultiblock copolymers can be formed, including: (S-B-EB)_(n),(S-E-EB-E)_(n), (S-B-EP-E)_(n), (S-B-EB-E)_(n), (S-B-EP-B)_(n),(S-B-EB-B)_(n), (S-E-E-EP)_(n), (S-E-E-EB)_(n), (S-B-E-EP)_(n),(S-B-E-EB)_(n), (S-B-B-EP)_(n), (S-B-B-EB)_(n), (S-E-B-EB)_(n),(S-E-B-EP)_(n), (S-EB-EB)_(n), (S-EP-EP)_(n), (S-E-EB-EB)_(n),(S-E-EP-EP)_(n), (S-E-EB-EP)_(n), (S-B-EB-EB)_(n), (S-B-EP-EP)_(n), andthe like.

[0153] The Z and A portions of the linear and star-shaped multiblockcopolymers are incompatible and form a two or more-phase systemconsisting of sub-micron glassy domains (A) interconnected by flexible Zchains. These domains serve to crosslink and reinforce the structure.This physical elastomeric network structure is reversible, and heatingthe polymer above the softening point of the glassy domains temporarilydisrupt the structure, which can be restored by lowering thetemperature.

[0154] It should be noted that when the A to Z ratios fallssubstantially below about 30:70, various properties such as elongation,tensile strength, tear resistance and the like can decrease whileretaining other desired properties, such as gel rigidity, flexibility,elastic memory.

[0155] In general, for these block copolymers, the various measuredviscosities of 5, 10, 15, and 20, weight percent solution values intoluene at 30° C. can be extrapolated to a selected concentration. Forexample, a solution viscosity of a 5 weight percent copolymer solutionin toluene can be determined by extrapolation of 10, 15, and 20 weightpercent measurements to 5 weight percent concentration.

[0156] The Brookfield Viscosities can be measured at various neatpolymer concentrations, for example, the selected high viscosity linearmultiblock copolymers in (I) can have a typical Brookfield Viscosityvalue of a 20 weight percent solids solution in toluene at 25° C. ofabout 1,800 cps and higher, and advantageously about 2,000 cps andhigher. Typically, the Brookfield Viscosity values can range from atleast about 1,800 to about 16,000 cps and higher. More typically, theBrookfield Viscosity values can range from at least about 1,800 cps toabout 40,000 cps and higher. Still more typically, the BrookfieldViscosity values can range from at least about 1,800 cps to about 80,000cps and higher. Due to structural variations between the multiblock andstar-shaped copolymers, the high viscosity star-shaped or radialcopolymers, typically, may exhibit a lower Brookfield Viscosity valuethan its counterpart linear multiblock copolymers. However, when themultiblock copolymers are considered as star-shaped or branched, than atequal branch lengths, the solution viscosities of the multiblockcopolymers and branched copolymers are about the same or equivalent.

[0157] In all cases, the molecular chain lengths (molecular weights) ofthe multiblock and star-shaped (or radial) copolymers (I) must besufficient to meet the high solution Brookfield Viscosities requirementsdescribed herein that is necessary for making the soft, strong andextreme tear resistant gels.

[0158] The copolymers (I) selected have Brookfield Viscosity valuesranging from about 1,800 cps to about 80,000 cps and higher whenmeasured at 20 weight percent solution in toluene at 25° C., about 4,000cps to about 40,000 cps and higher when measured at 25 weight percentsolids solution in toluene. Typical examples of Brookfield Viscosityvalues for star-shaped copolymers at 25 weight percent solids solutionin toluene at 25° C. can range from about 3,500 cps to about 30,000 cpsand higher; more typically, about 9,000 cps and higher. Otheradvantageous multiblock and multiblock star-shaped copolymers canexhibit viscosities (as measured with a Brookfield model RVT viscometerat 25° C.) at 10 weight percent solution in toluene of about 400 cps andhigher and at 15 weight percent solution in toluene of about 5,600 cpsand higher. Other advantageous multiblock and star-shaped copolymers canexhibit about 8,000 to about 20,000 cps at 20 weight percent solidssolution in toluene at 25° C. Examples of most advantageous highviscosity linear multiblock copolymers can have Brookfield viscositiesat 5 weight percent solution in toluene at 30° C. of from about 40 toabout 50, 60, 70, 80, 90, 100. 120, 150, 200 cps and higher, whileviscosities of star-shaped multiblock copolymers are 150 cps and higher.

[0159] Examples of high viscosity multiblock copolymers (I) having twoor more midblocks are Kuraray's (S-E-EP-S) 4033, 4045, 4055 and 4077hydrogenated styrene isoprene/butadiene block copolymers, morespecifically, hydrogenated styrene block polymer with2-methyl-1,3-butadiene and 1,3-butadiene. Kuraray's 4055 (S-E-EP-S)multiblock copolymer and 4077 exhibit viscosities at 5 weight percentsolution in toluene at 30° C. of about 90 cps to about 120 cps and about200 to about 380 cps respectively. At 10 weight percent SEEPS 4055 isabout 5,800 cps and higher. Other linear and star multiblock copolymers(I) such as (S-E-EP-S), (S-E-EP-E-S), (S-B-EP-S), (S-E-EB-S),(S-EB-EP-S), (S-E-EP-EB-S), (S-B-EB-S), (S-E-EB-E-S), (S-B-EP-E-S),(S-B-EB-E-S), (S-B-EP-B-S), (S-B-EB-B-S), (S-E-E-EP-S), (S-E-E-EB-S),(S-B-E-EP-S), (S-B-E-EB-S), (S-B-B-EP-S), (S-B-B-EB-S), (S-E-B-EB-S),(S-E-B-EP-S), (S-EB-EB-S), (S-EP-EP-S), (S-E-EB-EB-S), (S-E-EP-EP-S),(S-E-EB-EP-S), (S-B-EB-EB-S), (S-B-EP-EP-S), (S-B-EB-EP-S),(S-B-EP-EB-S), (S-E-EP-E-EP-S), (S-E-EP)_(n), (S-E-EP-E)_(n),(S-B-EP)_(n), (S-E-EB-S)_(n), (S-EB-EP-)_(n), (S-E-EP-EB)_(n),(S-B-EB)_(n), (S-E-EB-E)_(n) can also exhibit viscosities at 5 weightpercent solution in toluene at 30° C. of from less than about 100 toabout 200, 300, 400, 500, 600, 700, 800, 900, 1,000, 1,200, 1,300,1,600, 1,800, 2,000 cps and higher.

[0160] The copolymer (I) forming the invention gels can have a broadrange of A end block to Z center block ratio of about 20.80 or less toabout 40:60 or higher. The A:Z weight ratios can range from lower thanabout 20:80 to above about 40:60 and higher. More specifically, thevalues can be 19:81, 20:80, 21:79, 22:78, 23:77, 24:76, 25:75, 26:74,27:73, 28:72, 29:71, 30:70, 31:69, 32:68, 33:67, 34:66, 35:65, 36:64,37:63, 38:62, 39:61, 40:60, 41:59, 42:58, 43:57, 44:65, 45:55, 46:54,47:53, 48:52, 49:51, 50:50, 51:49 and etc. Other ratio values of lessthan 19:81 or higher than 51:49 are also possible. Broadly, the styreneblock to elastomeric block ratio A:Z of the high viscosity multiblockand star copolymers (I) is about 20:80 to about 40:60 or higher, lessbroadly about 31:69 to about 40:60, preferably about 32:68 to about38:62, more preferably about 32:68 to about 36:64, particularly morepreferably about 32:68 to about 34:66, especially more preferably about33:67 to about 36:64, and most preferably about 30:70.

[0161] Theory notwithstanding, the multiblock copolymer gel propertiescan be attributed to the additional blocks affecting the separatepolymer phases, the additional blocks affecting the heterophasestructure, the additional blocks affecting the interfacial regionsbetween phases of the multiblock polymers, the additional blocks forminga separate phase or inducing the formation of additional separatephases, or the high molecular weight and combination of high styrenecontent of the block copolymer Due to the additional number of midblocksof the copolymers (I), the differences in solubility parameters between(A) and (Z) becomes greater than the solubility parameters differencesbetween (A) and (D) of triblock copolymers, where D denotes the lonemidblock polymer chain. Moreover, the presence of additional midblocksof ethylene, propylene, butylene, ethylene-propylene, orethylene-butylene may contribute to stress-induced crystallization. Thismay explain why as the viscosity of the multiblock copolymers isincreased to a higher level, the appearance of the invention gels changefrom clear to more translucent white.

[0162] The invention gels of the present invention resist tearing undertensile loads or dynamic deformation in that when cut or notched, the“crack” made on the gel deep surface does not readily propagate furtherunder dynamic deformation or tensile loads. Unlike triblock copolymergels, such as (SEBS) and (SEPS) gels which possess high tensile strengthand will catastrophically snap apart into two reflective clean smoothsurfaces when cut or notched under tensile or dynamic loads.Furthermore, when elongated, the invention gels can exhibit two or moredraw plateaus and can possess high tensile strength and rapid returnfrom high extension without noticeable set or deformation. As observed,the invention gels can be stretched by a first tensile load with uniformdeformation to a measured length, upon the application of higher tensileloads, the gel can be further extended without breaking. Upon release,the gel returns immediate to its original shape and any necking quicklydisappears. Again, theory notwithstanding, the additional drawingplateaus of the gel may be attributed to yielding of crystalliteformations ethylene or propylene components in the gel or yield ofinduced interfacial regions of concentrated ethylene or propylenebetween the domains which during extension absorbs the elastic energy.Likewise, the resistance to tear propagation of the invention gels whennotched under tensile load can be attributed to yielding of the gelmidblock components, yielding of additional phases, or yielding ofinterfacial regions before rupture or deformation of the (A) domains cantake place.

[0163] Additionally, shearing, heating or cooling form the molten statecan alter the gels' state The invention gels can be made to exhibit longelastomeric recovery times. Such gels can be used effectively insuppressing low frequency vibrations and for absorbing energy. Theunusual properties of the invention gels can be attributed to alteringdifferent phase or interfacial arrangements of the domains of themultiblock copolymers. The presence of polyethylene and crystallinity inblock copolymers can be determined by NMR and DSC.

[0164] Physical measurements (NMR and DSC) of typical commercial KratonG 1651, Septon 2006, Septon 4033 and Septon 4055 block were performed.Two types of ¹³C NMR spectra data were collected. The gated decoupledexperiment provided quantitative data for each type of carbon atom. TheDEPT experiment identified each type of carbon atom having attachedprotons. The DEPT data allowed assignment of the resonances in the gateddecoupled experiment, which was then integrated for quantitation of thedifferent types of midblock and end groups in each polymer tested

[0165] The relative quantities of each type of carbon group in thevarious polymers were found. The uncertainty associated with thesemeasurements is estimated as ±3 percentage units. Only the Kraton 1651spectrum had resonances below about 20 ppm. These resonances, at10.7-10.9 ppm, were assigned to the butylene methyl group anddistinguish the SEBS polymer from the SEPS and SEEPS types of polymer(36). Only the Septon 2006 spectrum lacked the resonance at about 20 ppmthat is characteristic of polyethylene units (defined here as threecontiguous CH₂ groups), and this feature distinguishes the SEPS polymerfrom the SEBS and SEEPS polymers (36). There were additional differencesbetween the spectra. The Septon 2006 and the Septon 4033 and 4055spectra all showed resonances at 20 ppm; whereas the spectrum of Kraton1651 was missing this resonance The 20 ppm peak is characteristic of themethyl group of a propylene subunit, which is present in SEPS and SEEPSpolymers but absent in the SEBS polymer. There were also a methylenepeak, at 24.6 ppm, and a methine peak at 32.8 ppm, in all of the Septonspectra but not in the Kraton 1651 spectra. These resonances also arisefrom the propylene subunit.

[0166] The chemical shifts, relative intensities, and relativeintegrations were the same for the spectra of the Septon 4033 and Septon4055, indicating that these two polymeric compositions are identicalbased on NMR spectroscopy.

[0167] DSC of ASTM D3417-99 was modified to provide conditions for thesamples to have the best possible chance to exhibit any crystallinity.The protocol was as follows: (1) heat to 140° C. @ 10° C./min., (2) coolto 0° C. @ 2° C./min., (3) place in freezer for 1 week, (4) heat to 140°C. @ 1° C./min, and (5) cool to 0° C. @ 1° C./min.

[0168] This protocol was used with the exception that the samples wereleft in the freezer for approximately 2 months, instead of 1 week,because the DSC equipment broke during the week after the first run andrequired some time for repair. This delay is not expected to havenegatively impacted the results of the experiment.

[0169] Two HDPE reference samples gave clearly defined crystallizationexotherms and fusion endotherms, allowing calculation of heats ofcrystallization and fusion. These results showed that the equipment andmethodology were fully functional, and this check was performed dailyduring DSC operation. Of the samples, only Kraton 1651 showeddiscernable transitions for both crystallization and fusion. The Septon2006 showed no discernable transitions, which is consistent with itsSEPS structure being entirely amorphous. The Septons 4033 and 4055showed crystallization exotherms.

[0170] The heats of crystallization for the Kraton 1651 and Septons 4033and 4055 were small, below about 3 J/g, indicating that small amounts ofcrystallinity are present in these polymers. The DSC data show:

[0171] Kraton 1651: crystallization exotherm peak at 18.09° C.,crystallization exotherm—mass normalized enthalpy (J/g) of 1.43, fusionendortherm peak at 34.13° C., and Fusion Endotherm—mass normalizedenthalphy J/g of 15.17.

[0172] Septon 2006: crystallization exotherm peak (not detected),crystallization exotherm—mass normalized enthalpy (not detected), fusionendortherm peak NONE, and Fusion Endotherm—mass normalized enthalphy(not detected).

[0173] Septon 4033: crystallization exotherm peak at 2.86° C.,crystallization exotherm—mass normalized enthalpy (J/g) of 3.00, fusionendortherm peak (not detected), and Fusion Endotherm—mass normalizedenthalphy (not detected).

[0174] Septon 4055: crystallization exotherm peak at 14.4° C.,crystallization exotherm—mass normalized enthalpy (J/g) of 1.32, fusionendortherm peak (not detected), and Fusion Endotherm—mass normalizedenthalphy (not detected).

[0175] Aldrich 13813JU polyethylene reference: crystallization exothermpeak at 119.72° C., crystallization exotherm—mass normalized enthalpy(J/g) of 174.60, fusion endortherm peak at 130.70° C., and FusionEndotherm—mass normalized enthalphy J/g of 189.90.

[0176] Plasticizers (II) particularly advantageous for use in practicingthe present invention are will known in the art, they include rubberprocessing oils such as paraffinic and naphthenic petroleum oils, highlyrefined aromatic-free paraffinic and naphthenic food and technical gradewhite petroleum mineral oils, and synthetic liquid oligomers ofpolybutene, polypropene, polyterpene, etc The synthetic series processoils are high viscosity oligomers which are permanently fluid liquidnonolefins, isoparaffins or paraffins of moderate to high molecularweight.

[0177] Incorporated herein by reference, in part, is the “Physical andChemical Properties of Mineral Oils That Affect Lubrication”, ®Copyright Herguth Laboratories, Inc. 1995, which is a review of mineraloils and terms for the tribologist working in the field of Tribology. Afew of the terms are provided for clear reading of the description ofthe invention as follows:

[0178] Viscosity is the property of a fluid that causes it to resistflow, which mechanically is the ratio of shear stress to shear rate.Viscosity may be visualized as a result of physical interaction ofmolecules when subjected to flow. Lubricating oils have long chainhydrocarbon structures, and viscosity increases with chain length. Theunit of absolute or dynamic viscosity is Force/Area×Time. The basic SIunit is Pascal×second Pa s (or Ns m−2). Mineral oils are typically 0.02to 0.05 Pa.s at 40 degree C. 1 mPa.s=1 Centipoise (cP) cP is commonlyused for absolute viscosity. The symbol for viscosity is usually u. Whengravity is used to cause flow for the viscosity measurement, the densityp of the oil is involved and kinematic viscosity is reported=u/p. Thebasic SI unit is meter²/second (m2 s−1). Also 1 cm2 s−1=1 Stoke (St),and 1 mm2 s−1=1 centiStoke (cSt), cSt is commonly used for kinematicviscosity. Viscosity (by ASTM D445) of industrial lubricants is commonlyclassified using the International Standard Organization Viscosity Grade(ISOVG) system, which is the average viscosity in centiStokes (cSt) at40 degree C. For example, ISOVG 32 is assigned to oils with viscositybetween 28.8 and 35.2 cSt at 40 degree C.

[0179] Viscosity Index (VI) is a commonly used expression of an oil'schange of viscosity with temperature. VI is based on two hypotheticaloils with arbitrarily assigned VI's of 0 and 100. The higher theviscosity index the smaller the relative change in viscosity withtemperature. A less arbitrary indication of the change in viscosity withtemperature is the viscosity temperature coefficient. For 40 to 100degree C. it is: Viscosity (cSt) at 40 degree C. minus Viscosity (cSt)at 100 degrees C.=C−1, divided by the Viscosity (cSt) at 40 degrees C.

[0180] Vapor pressure is the pressure exerted by a vapor on a liquidwhen it is in equilibrium with its own vapor. The higher theconcentration of low molecular weight fractions, the greater the vaporpressure. Vapor pressure is reported as a pressure at a specifiedtemperature. Volatility is reported as percent evaporative weight lossand is measured by ASTM method D-972.

[0181] Flash point is an indication of the combustibility of the vaporsof a mineral oil, and is defined as the lowest temperature at which thevapor of an oil can be ignited under specified conditions. Flash pointis clearly related to safety. Flash point of lubricating oils ismeasured using ASTM D 92. An open cup of oil is heated at a specificrate while periodically passing a small flame over its surface. Theflash point is considered to be the lowest temperature at which the oilvapors will ignite, but not sustain a flame.

[0182] Surface tension is the surface energy between a liquid and itsown vapor, or air, or a metal surface. The word tension comes from theforce that resists any attempt to increase the surface area. Surfacetension is thought to be a factor in the ability of an oil to “wet” asurface, in emulsion stability, and in the stability of dispersedsolids. However, “wetting” has been found to be a complex phenomenoninvolving oleophobic and oleophilic films on the metal surface. Someadditives markedly change surface tension.

[0183] Paraffinic oils are straight chain or branched aliphatichydrocarbons belonging to the series with the general formula CnH2n+2.Paraffin's are saturated with respect to hydrogen. A typical paraffinicoil molecule with 25 carbon and 52 hydrogen atoms has a molecular weightof 352. Very high molecular weight paraffins are solid waxes, alsodissolved in small amounts of mineral oils

[0184] Naphthenic or alicyclic oils have the characteristics ofnaphthenes, which are saturated hydrocarbons of which the moleculescontain at least one closed ring of carbon atoms.

[0185] Paraffins are relatively unreactive and thus have betteroxidation stability compared to naphthenes. In general, paraffins have ahigher viscosity index than naphthenics

[0186] Physical and Chemical Properties of Mineral Oils That AffectLubrication have been delt with by Douglas Godfrey of HerguthLaboratories, Inc. 1995 which describes viscosity as being the propertyof a fluid that causes it to resist flow, which mechanically is theratio of shear stress to shear rate. Viscosity may be visualized as aresult of physical interaction of molecules when subjected to flow.Lubricating oils have long chain hydrocarbon structures, and viscosityincreases with chain length. Viscosity of an oil film, or a flowingcolumn of oil, is dependent upon the strong absorption of the firstlayer adjacent to the solid surfaces, and the shear of adjacent layers.

[0187] Specific gravity is used which is ratio of the mass of a givenvolume to the mass of an equal volume of water. Therefore, specificgravity is dimensionless. The specific gravity of mineral oils alsovaries from 0.86 to 0.98 since the specific gravity of water is 1 at15.6 degree C. Specific gravity decreases with increased temperature anddecreases slightly as viscosity decreases for similar compositions.Reference 5 (pp. 482-484) gives the specific gravity of 81 mineral oilsat 15.6 degree C.

[0188] Bulk modulus expresses the resistance of a fluid to a decrease involume due to compression. A decrease in volume would increase density.Compressibility is the reciprocal of bulk modulus or the tendency to becompressed. Bulk modulus varies with pressure, temperature, molecularstructure and gas content. Generally, mineral oils are thought to beincompressible. In high pressure hydraulic systems a high bulk modulusor low compressibility is required to transmit power efficiently anddynamically. Bulk modulus is determined by measuring the volume of anoil at various pressures or derived from density measurements at variouspressures. Bulk modulus can also be measured by the speed of sound inoils under various pressures. A discussion of bulk modulus and valuesare given in References 9 and 10 Since a graph of pressure versus volumegives a curve, the secant to the curve is used and is called IsothermalSecant Bulk Modulus.

[0189] Gases are soluble in mineral oils to a limited amount. The amountvaries with the type of gas and oil temperature. For example, 8 to 9% ofair, by volume, is soluble in mineral oil at room temperature and isinvisible. Dissolved gases affect oil viscosity, bulk modulus, heattransfer, oil and metal oxidation, boundary lubrication, foaming andcavitation. Boundary lubrication is improved by the oxygen in dissolvedair because it continuously repairs the protective oxide films onmetals. Dissolved oxygen is considered an important anti-scuffcomponent. The amount of dissolved gas become evident when gases comeout of solution vigorously when the oil is subjected to low pressures.

[0190] The amount of soluble gas is measured by ASTM D 2780 “Solubilityof Fixed Gases In Liquid Test”. This method physically separates the gasthrough an extraction process and measures the quantity volumetrically.This method allows for subsequent qualitative analysis of the extractedgas by any appropriate technique.

[0191] If the amount of a gas in oil exceeds saturation, small bubbleswill form, remain suspended, and the oil will appear hazy This is calledentrained gas. The bubbles slowly rise to the surface Bubbles of a gas,such as air, in an oil film cause holes that reduce oil film continuityand decrease the film's ability to prevent solid-to-solid contact.

[0192] The relative tendency of various oils to release entrained gas ismeasured by a gas bubble separation method ASTM D 3427. The method usesa cylinder-like test vessel with gas inlet and outlet ports. Air, oranother gas (if of interest), is introduced into the bottom of thevessel at a specified temperature and flow rate. At the end of sevenminutes the gas flow is stopped and the change in density as measured bya densitometer is recorded. The test is complete when the total volumeof entrained air is reduced to 0.20% by volume. The results are reportedas the time it took for the oil to attain this value.

[0193] Foaming is defined as the production and coalescence of gasbubbles on a lubricant surface. Foam may be a result of a variety ofproblems including air leaks, contamination, and over filling of sumps.Foaming can cause loss of oil out of a vent and serious operationalproblems in most lubricated systems. Excessive foam can starve bearingsand pumps of liquid lubricant (pump cavitation) causing failure, andcause poor performance in hydraulic systems. The foaming characteristicsof an oil are measured by ASTM D-892. Using a calibrated porous stone,air is blown into the bottom of a graduated cylinder for a specifiedtime. Immediately upon completion of the blowing period, the foam thathas formed on the top of the oil is measured. Ten minutes after thecompletion of the blowing period, an additional measurement is made ofthe remaining foam as the foam retention characteristics of the oil. Theresults are reported in milliliters.

[0194] Examples of representative commercially available plasticizingoils include Amoco® polybutenes, hydrogenated polybutenes, polybuteneswith epoxide functionality at one end of the polybutene polymer, liquidpoly(ethylene/butylene), liquid hetero-telechelic polymers ofpoly(ethylene/butylene/styrene) with epoxidized polyisoprene andpoly(ethylene/butylene) with epoxidized polyisoprene. Example of suchpolybutenes include: L-14 (320 Mn), L-50 (420 Mn), L-100 (460 Mn), H-15(560 Mn), H-25 (610 Mn), H-35 (660 Mn), H-50 (750 Mn), H-100 (920 Mn),H-300 (1290 Mn), L-14E (27-37 cst @ 100° F. Viscosity), H-300E (635-690cst @ 210° F. Viscosity), Actipol E6 (365 Mn), E16 (973 Mn), E23 (1433Mn), Kraton L-1203, EKP-206, EKP-207, HPVM-2203 and the like. Example ofvarious commercially oils include: ARCO Prime (55, 70, 90, 200, 350, 400and the like), Duroprime and Tufflo oils (6006, 6016, 6016M, 6026, 6036,6056, 6206, etc), other white mineral oils include: Bayol, Bernol,American, Drakeol, Ervol, Gloria, Kaydol, Litetek, Lyondell (Duroprime55, 70, 90, 200, 350, 400, Ideal FG 32, 46, 68, 100, 220, 460), Marcol,Parol, Peneteck, Primol, Protol, Sontex, and the like. Oils useful inthe invention gel include: Witco 40 oil, Ervol, Benol, Blandol,Semtol-100, Semtol 85, Semtol 70, Semtol 40, Orzol, Britol, Protol,Rudol, Carnation, Klearol, 350, 100, 85, 70, 40, Pd-23, Pd 25, Pd28, FG32, 46, 68, 100, 220, 460, Duroprime Ds-L, Ds-M, Duropac 70, 90, Crystex22, Af-L, Af M, 6006, 6016, 6026, Tufflo 6056, Ste Oil Co, Inc: CrystalPlus 70, 200, 350, Lyondell: Duroprime DS L & M, Duropac 70, 90, Crystex22, Crystex AF L & M, Tufflo 6006, 6016; Chevron Texaco Corp: SupertaWhite Oil 5, Superta 7, 9, 10, 13, 18, 21, 31, 35, 38, 50, Penreco:Conosol 340, Conosol C-200, Drakeol 15, 13, 10, 10B, 9, 7, 5, 50,Peneteck Ultra Chemical Inc, Ultraol White 60Nf, Ultraol White 50Nf,Witco Hydrobrite 100, 550, 1000, and the like.

[0195] Selected amounts of one or more compatible plasticizers can beused to achieve gel rigidities of from less than about 2 gram Bloom toabout 1,800 gram Bloom and higher. Tack may not completely be dependentupon the amount of the glassy phase, by using selected amount of certainlow viscosity oil plasticizers, block copolymers of SEBS, SEEPS, SEPS,SEP_(n), SEB_(n), and the like, gel tack can be reduced or the gel canbe made non-tacky,

[0196] Major or minor amounts (based on 100 parts by weight of baseelastomer) of any compatible second plasticizers can be utilized informing the invention gel, but because of the non-tack property of theinvention gel, the major amount of first plasticizers used should be lowviscosity plasticizers having viscosities advantageously of not greaterthan about 30 cSt @ 40° C., for example 30, 29, 28, 27, 26, 25, 24, 23,22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3and the like. The invention gel tack decreases with decreasing oilviscosities of from about 30 to 3. Invention gels which are non-tacky tothe touch can be achieved using oils with viscosities of about 10 cSt @40° C. and less. Best result can be achieved using oils with viscositiesof about 6 and less. Oils of higher viscosities of from about 500 cSt @40° C. to about 30 produce higher and higher tack with increase inviscosities. Heat temperature set resistance improves with increase inoil viscosity. Oils with viscosities less than about 15 exhibit heat setat about 50° C. Therefore a combination of low viscosity oils to improvelow tack and high viscosity oils to improve set can be achieved byblending various oils having the desired viscosities for the desired enduse. The disassociation of polystyrene is about 100° C. to about 135°C., the invention gels do not melt below the disassociation temperatureof polystyrene. It is important that fishing bait when stored in afishing box in the hot Sun at about 50° C. to about 58° C. do not suffersubstantial heat set as tested at these temperatures in a 108° U bendfor one hour.

[0197] It has been found that the lower the oil viscosity, the lower theheat set of the resulting gel composition and the higher the oilviscosity use in the gel compositions of the invention, the higher theheat set of the resulting gel composition. For example, if the firstplasticizer is less than about 50 SUS @ 100° F., the heat set of theresulting gel composition comprising 100 parts of (I) copolymers ofequal parts of SEEPS 4055 and Kraton G 1651 with about 600 parts byweight of the first plasticizer, the resulting is found to have a heatset less than that of a conventional PVC plastisol fishing bait at about50° C. However, as the 50 Vis SUS @ 100° F. oil of the formulation isgradually replaced with a higher viscosity oil of about 80-90 SUS @ 100°C., the heat set deformation improves with increasing amounts of thehigher viscosity oil. In order to obtain equal heat set performance asconventional PVC plastisol fishing bait, the first and secondplasticizers would have to be of equal amounts in the gel composition.Replacing the first plasticizer with a greater amount would increase thegel tack. If tack is not of great concern, then a higher amount of thesecond plasticizers would be beneficial for improving heat set at higherand higher temperatures to the point that the second plasticizers canreach greater than 2525 SUS @ 100° C. (Ideal FG 100, 220, or 460 oil)the resulting gel composition would not exhibit set at even temperaturesgreater than 400° F.

[0198] The cited first plasticizers with or without one or more secondplasticizers can be used in sufficient amounts to achieve a gel rigidityof from about 20 gram Bloom to about 1,800 gram Bloom. The secondplasticizers in effective amounts in combination with the firstplasticizers can provide a greater temperature compression set than agelatinous composition having the same rigidity formed from the firstplasticizers alone. The second plasticizers when used can provide agreater temperature compression set than a gelatinous composition havingthe same rigidity formed from the first plasticizers alone or formedfrom a combination of the first plasticizers and the secondplasticizers. The first plasticizers being in effective amounts withsaid second plasticizers can provide a Gram Tack lower than a gelatinouscomposition having the same rigidity formed from the second plasticizersalone.

[0199] Generally, plasticizing oils with average molecular weights lessthan about 200 and greater than about 700 may also be used (e.g H-300(1290 Mn)). It is well know that minor and sufficient amounts of VitaminE is added to the described commercially available oils during bulkprocessing which is useful as a oil stabilizer, antioxidant, andpreservative.

[0200] Of all the factors, the amount of plasticizing oils can becontrolled and adjusted advantageously to obtain substantially highertear and tensile strength gels. The improvements in tensile strength ofthe invention gels are accompanied by corresponding increase in gelrigidity as the amount of plasticizing oils are lowered until therigidity of the invention gels becomes much higher than that of the gumswhich surround the teeth. Although higher tensile strengths can beobtained as the amount of plasticizing oils in the gel approaches zero,the tensile strength of the floss, however, must be maintained at anacceptable gel rigidity (at sufficient high plasticizing oil levels) inorder to be as soft as the gums required for flossing. For example, therigidities of a gel containing 100, 200, or 300 parts by weight of oilis much higher than a gel containing 300, 400, 500, 600, 800, or 900parts of oil.

[0201] These gels can exhibit a larger unit lateral contraction at thesame elongation per unit of length as their counterpart parent gels fromwhich the invention gels are derived or formed. This property wouldallow a same unit volume of gel when elongated as its parent to easilywedge between the teeth when flossing. It would seem that a gel havingthe 10 cm³ volume made from a ratio of 100 parts by weight of copolymerand 400 parts plasticizer would have a unique macro volumeconfigurations that is at equilibrium with the plasticizer which is muchlike a 3-D fingerprint which is uniquely different from any other gel ofa different copolymer to plasticizer ratio. Reducing the plasticizercontent of a ratio 100:400 gel to a 100:300 ratio of copolymer toplasticizer will decrease the amount of plasticizer, but the originalmacro volume configurations will remain the same.

[0202] Speculative theories not withstanding, configurations may takethe form of (1) swiss cheese, (2) sponge, (3) the insides of a loaf ofbread, (4) structures liken to ocean brain corals, (5) large structuresand small structures forming the 3-D gel volume landscape, (6) the outerheated surface which cools faster than the inner volumes of the gelduring its cooling histories may have a patterned crust (rich in Amicro-phases) like that of a loaf of bread and the inner volume may havemuch like 1-5, and (7) the many different possible structures areunlimited and volume landscapes may be interconnected at the macro-levelby threads or micro-strands of Z micro-phases.

[0203] The amount of plasticizer extracted can advantageously range fromless than about 10% by weight to about 90% and higher of the totalweight of the plasticizer. More advantageously, the extracted amounts ofplasticizer can range from less than about 20% by weight to about 80% byweight of the total plasticizer, and still more advantageously, fromabout 25% to about 75%. Plasticizing oils contained in the inventiongels can be extracted by any conventional methods, such as solventextraction, physical extraction, pressure, pressure-heat, heat-solvent,pressure-solvent-heat, vacuum extraction, vacuum-heat extraction, vacuumpressure extraction, vacuum-heat-pressure extraction, vacuum-solventextraction, vacuum-heat-solvent-pressure extraction, etc. The solventsselected, should be solvents which do not substantially disrupt the Aand Z phases of the (I) copolymers forming the invention gels. Anysolvent which will extract plasticizer from the gel and do not disruptthe A and Z phases can be utilized Suitable solvents include alcohols,primary, secondary and tertiary alcohols, glycols, etc., examplesinclude methanol, ethanol, tetradecanol, etc. Likewise, the pressuresand heat applied to remove the desired amounts of oils should not besufficient to disrupt the A and Z domains of the (I) copolymers To forma lower rigidity gel, the simplest method is to subject the gel to heatin a partial vacuum or under higher vacuum for a selected period oftime, depending on the amount of plasticizer to be extracted.

[0204] Surprisingly, as disclosed in my application Ser. No. 09/896,047filed Jun. 30, 2001, oil extraction from the invention gels can beachieved with little or no energy in the presence of one or moresilicone fluids to almost any degree. A theory can be made to explainthe physics involved in the extraction process which reasoning is asfollows: (1) When water is placed in contact with an oil extended gel,the gel will not over time exhibit weight loss (2) When oil is add to acolumn of water in a test tube, the oil will separate out and find itslevel above the column of water. (3) The surface tension of water at 25°C. is about 72.0 mN/m. (4) The surface tension of oil (mineral oil) at25° C. is about 29.7 mN/m. (5) The surface tension of silicone fluid at25° C. range from abut 16 to abut 22 mN/m (for example: the surfacetension of 100 cSt silicone fluid at STP is 20.9 mN/m). (6) The densityof oil is less than the density of silicone fluid, silicone grease,silicone gel, and silicone elastomer. (7) Oil is not a polar liquid andis highly compatible with the rubber phase of the oil gel formingpolymer. (8) Silicone is polar and not compatible with the polymer'srubber phase.

[0205] The molecules of a liquid oil drop attract each other. Theinteractions of an oil molecule in the liquid oil drop are balanced byan equal attractive force in all directions. Oil molecules on thesurface of the liquid oil drop experience an imbalance of forces at theinterface with air. The effect is the presence of free energy at thesurface. This excess energy is called surface free energy and isquantified as a measurement of energy/area. This can be described astension or surface tension which is quantified as a force/lengthmeasurement or m/Nm.

[0206] Clearly gravity is the only force pulling on the extracted oilfrom the gel in the presence of silicone fluid at the gel-petri dishinterface in the examples below. In the case of gel samples in the petridishes in contact with silicone fluids, the extracted oil are collectedon the top surface layer of the silicone fluid while the silicone fluidmaintain constant contact and surrounds the gel sample. In the case ofgel placed in a test tube of silicone fluid of different viscosity, theoil is extracted and migrates and collect at the top of the siliconefluid surface while the gel reduces in volume with time. The oilextraction process in silicone is accompanied by buoyant forces removingthe extracted oil from the surroundings of the gel constantlysurrounding the gel with fresh silicone fluid while in the example ofalcohol, since the oil is heavier, the oil is maintained and surroundsthe gel sample forming a equilibrium condition of oil surround the gelsample while keeping the alcohol from being in contact with the gelsample. Therefore in order to use alcohol to extract oil from a gelsample, the extracted oil must be constantly removed from the oilalcohol mixture as is the case during soxhlet extraction which processrequires additional energy to pump the oil-alcohol mixture away from thesample and removing the oil before forcing the alcohol back to the gelsample surface to perform further extraction.

[0207] Silicone fluid is efficient and useful for extracting oil formoil gel compositions with the assistance of gravity and buoyancy of oilin the silicone fluids.

[0208] It is very difficult to extract, separate, or remove oil from anoil gel composition by positive or vacuum pressure or heat while usinglittle or no energy and because of the affinity of the rubber midblockfor oil, not even the weight of a two ton truck resting on a four squarefoot area (placing a layer of gel between four pairs of one foot squareparallel steel plates one set under each of the truck tire resting onthe gels) can separate the oil from the gel composition.

[0209] The use of silicone fluids of various viscosity acts as a liquidsemi porous membrane when placed in constant contact with an oil gelcomposition will induce oil to migrate out of the gel composition. Bythe use of gravity or oil buoyancy, no energy is required run the oilextraction process.

[0210] In the case of the invention gels of this application made in theshape of a fishing bait in contact with silicone fluid, the elastomer orrubber being highly compatible with the oil, holds the oil in placewithin the boundary of the rubber molecular phase. It is this affinityof the (i) rubber and oil molecules and (ii) the attraction of oilmolecules for each other that prevents the oil from bleeding out of thesurface of the gel body. There exist then, at the surface of the gelseveral types of surface tensions of: (iii) oil-air surface tension,(iv) oil-rubber surface tension, (v) rubber-air surface tension, (vi)rubber/oil-air surface tension, and (vii) rubber-rubber surface tension.Other forces acting on the gel are: the elastic force of the polymernetwork pulling inwards, similar to stretched out rubber bands, which isin equilibrium with the oil molecules' attraction to the rubbermolecules of the polymer network. In the case of SBS, the lowercompatibility of the midblock butadiene with oil, once a gel is made,the SBS network immediately contracts due to elastic forces to produceoil bleeding which is evidence of the poor compatibility of the rubberblock for the oil molecules.

[0211] The intermolecular forces that bind similar molecules togetherare called cohesive forces. Intermolecular forces that bind a substanceto a surface are called adhesive forces.

[0212] When two liquids are in contact such as oil and silicone fluid,there is interfacial tension. The more dense fluid is referred to hereinas the “heavy phase” and the less dense fluid is referred to as the“light phase”. The action at the surface of the oil extended polymer gelsurface when brought into contact with silicone fluid is as follows: adrop of silicone fluid when placed on the flat surface of a oil extendedpolymer gel will wet the gel surface and spread over a larger area ascompared to a drop of oil placed on the same gel surface. Because thesurface free energy of the silicone fluid in contact with the gelsurface is lower than the surface free energy of the oil, the siliconefluid has the ability to displaces the oil from the surface of the gel.

[0213] The invention gels can optionally comprise selected major orminor amounts of one or more polymers or copolymers (III) provided theamounts and combinations are selected without substantially decreasingthe desired properties. The polymers and copolymers can be linear,star-shaped, branched, or multiarm; these including: (SBS)styrene-butadiene-styrene block copolymers, (SIS)styrene-isoprene-styrene block copolymers, (low styrene content SEBSsuch as Kraton 1650 and 1652) styrene-ethylene-butylene-styrene blockcopolymers, (SEP) styrene-ethylene-propylene block copolymers, (SEPSKraton RP-1618) styrene-ethylene-propylene-styrene block copolymers,(SB)_(n) styrene-butadiene and (SEB)_(n), (SEBS)_(n), (SEP)_(n),(SI)_(n) styrene-isoprene multi-arm, branched or star-shaped copolymers,polyethyleneoxide (EO), poly(dimethylphenylene oxide) and the like.Still, other (III) polymers include homopolymers which can be utilizedin minor amounts; these include: polystyrene, polybutylene,polyethylene, polypropylene and the like.

[0214] In the case of high molecular weight and combination of highstyrene content of the block copolymer which may be the reason forimprove tear and fatigue resistance, these properties may be achievedand maintained by blending (I) copolymers of SEEPS with (III) copolymersof SBS (Kraton D 1101, 1144, 1116, 1118, 4141, 4150, 1133, 1184, 4158,1401P, 4240, and KX219), SEBS (G1651, 1654).

[0215] Other (III) polymers useful in the invention gels include: oftrifluoromethyl-4,5-difuoro-1,3-dioxole and tetrafluoroethylene,polytetrafluoroethylene, maleated poly(styrene-ethylene-butylene),maleated poly(styrene-ethylene-butylene)n, maleatedpoly(styrene-ethylene-butylene-styrene), maleatedpoly(styrene-ethylene-propylene)n, maleatedpoly(styrene-ethylene-propylene-styrene), poly(dimethylphenylene oxide),poly(ethylene-butylene), poly(ethylene-propylene),poly(ethylene-styrene) interpolymer made by metallocene catalysts, usingsingle site, constrained geometry addition polymerization catalysts,poly(styrene-butadiene), poly(styrene-butadiene)n,poly(styrene-butadiene-styrene), poly(styrene-ethylene-butylene),poly(styrene-ethylene-butylene)n,poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-propylene), poly(styrene-ethylene-propylene)n,poly(styrene-ethylene-propylene-styrene), poly(styrene-isoprene),poly(styrene-isoprene)n, poly(styrene-isoprene-styrene),poly(styrene-isoprene-styrene)n, polyamide, polybutylene, polybutylene,polycarbonate, polydimethylsiloxane; polyethylene vinyl alcoholcopolymer, polyethylene, polyethyleneoxide, polypropylene, polystyrene,polyvinyl alcohol, wherein said selected copolymer is a linear, radial,star-shaped, branched or multiarm copolymer, wherein n is greater thanone

[0216] When the selected (III) polymers and copolymers contain greaterglassy block of styrene content of 33 and higher, such may be effectiveto provide a Gram Tack lower than a gelatinous composition having thesame rigidity formed from the (I) block copolymers and correspondingfirst plasticizers alone or the first plasticizers with a secondplasticizers. The selected component (III) polymers of polystyreneforming a styrene content of 33 and higher when used in effectiveamounts may provide a greater temperature compression set than agelatinous composition having the same rigidity formed from the (I)block copolymers and corresponding first plasticizers alone or the firstplasticizers with a second plasticizer.

[0217] On the other hand, the lower viscosity first plasticizer canimpart lower Gram Tack to the invention gels than an increase of styrenecontent of the (I) copolymers or (III) polymers and copolymers. The lowtack and non tacky invention gels can be made from one or more linear,branched, star-shaped (radial), or multiarm block copolymers or mixturesof two or more such block copolymers having one or more midblock polymerchains which invention gels have use as articles with high tearpropagation resistance. The invention gels also possess high tensilestrength and rapid return from high extension and can exist in analtered state of delay elastomeric recovery as it regains its originalshape following high extensions or dynamic deformations. The inventiongels also exhibit low set, high dimensional stability, crack, tear,craze, and creep resistance, excellent tensile strength and highelongation, long service life under shear, stress and strain and capableof withstanding repeated dynamic shear, tear and stress forces,excellent processing ability for cast molding, extruding, fiber formingfilm forming and spinning, non-toxic, nearly tasteless and odorless,soft and strong, optically clear, highly flexible, possessing elasticmemory, substantially with little or no plasticizer bleedout, and havinglow or no tack in contact with human hand which reduction in tackinesscan be measured. The non tacky and optical properties of the inventiongels do not rely on powders or surface activation by additives toestablish their non-tackiness The invention gels' non-tackinesspervasive the gels' entire bulk or volume. No matter how deep or inwhich direction a cut is made, the invention gels are non tackythroughout (at all points internally as well as on the gels' surface).Once the gel is cut, the invention gel immediately exhibitsnon-tackiness at its newly cut surface. Hence, the homogeneity of thenon-tackiness and optical properties of the invention gels are notknown.

[0218] Example of (III) polymers, copolymers, and blends include: (a)Kraton G 1651, G 1654X; (b) Kraton G 4600; (c) Kraton G 4609; othersuitable high viscosity polymer and oil s include: (d) Tuftec H 1051;(e) Tuftec H 1041; (f) Tuftec H 1052; (g) low viscosity Kuraray SEEPS4033 (hydrogenated styrene isoprene/butadiene block copolymers, morespecifically, hydrogenated styrene block polymer with2-methyl-1,3-butadiene and 1,3-butadiene); (h) Kuraray SEBS 8006; (i)Kuraray SEPS 2005; (j) Kuraray SEPS 2006, and (k) blends (polyblends) of(a)-(h) with other polymers and copolymers include: (1) SEBS-SBS; (2)SEBS-SIS; (3) SEBS-(SEP); (4) SEBS-(SEB)_(n); (5) SEBS-(SEB)_(n); (6)SEBS-(SEP)_(n); (7) SEBS-(SI)_(n); (8) SEBS-(SI) multiarm; (9)SEBS-(SEB)_(n); (10) (SEB)_(n) star-shaped copolymer; (11) s made fromblends of (a)-(k) with other homopolymers include. (12)SEBS/polystyrene; (13) SEBS/polybutylene; (14) SEBS/polyethylene; (14)SEBS/polypropylene; (16) SEP/SEBS, (17) SEP/SEPS, (18) SEP/SEPS/SEB,(19), SEPS/SEBS/SEP, (20), SEB/SEBS (21), EB-EP/SEBS (22), SEBS/EB (23),SEBS/EP (24), (25) (SEB)_(n) s, (26) (SEP)_(n), (27) Kuraray 2007(SEPS), (28) Kuraray 2002, (SEPS), and the like.

[0219] Representative examples of commercial elastomers that can becombined with the multiblock and star-shaped copolymers (III) describedabove include: Shell Kratons D1101, D1102, D1107, D1111, D1112, D1113X,D1114X, D1116, D1117, D1118X, D1122X, D1125X, D1133X, D1135X, D1184,D1188X, D1300X, D1320X, D4122, D4141, D4158, D4240, G1650, G1652, G1657,G1701X, G1702X, G1726X, G1750X, G1765X, FG1901X, FG1921X, D2103, D2109,D2122X, D3202, D3204, D3226, D5298, D5999X, D7340, G1654X, G2701, G2703,G2705, G1706, G2721X, G7155, G7430, G7450, G7523X, G7528X, G7680, G7705,G7702X, G7720, G7722X, G7820, G7821X, G7827, G7890X, G7940, G1730(SEPSEP), FG1901X and FG1921X. Kuraray's SEPS, SEP/SEPS or SEP/SEB/SEPSNos. SEP 1001, SEP 1050, 2027, 2003, SEPS 2006, SEPS 2023, SEPS 2043,SEPS 2063, SEPS 2050, SEPS 2103, SEPS 2104, SEPS 2105, SEBS 8004, SEBS8007, H-VS-3 (S-V-EP-S) and the like. Dow poly(ethylene-styrene) randomcopolymers (interpolymers) produced by metallocene catalysts, usingsingle site, constrained geometry addition polymerization catalystsresulting in poly(ethylene-styrene) substantially random copolymers suchas ESI-#1 thru #38, including ES16, ES24, ES27, ES28, ES28, ES30, ES44with styrene wt % of 15.7, 23.7, 27.3, 28.1, 39.6 & 43.9 respectively, Mcopolymers (ES53, ES58, ES62, ES63, and ES69 with styrene wt % of 52.5,58.1, 62.7, 62.8, and 69.2 respectively and crystallinity, %, DSC, basedon copolymer of 37.5, 26.6, 17.4, 22.9, 19.6 and 5.0 respectively), Scopolymers (ES72, ES73, and ES74 with styrene wt % of 72.7, 72.8, and74.3 respectively). Other grade copolymers include ES60 (melt index 0.1,0.5, 3, 10), ES20 (MI=0.1. 0.5, 3, 11).

[0220] The Brookfield Viscosity of a 5 weight percent solids solution intoluene at 30° C. of 2006 is about 27. Typical Brookfield Viscosities ofa 10 weight percent solids solution in toluene at 30° C. of Kuraray SEP1001, SEP 1050, SEPS 2007 SEPS 2063, SEPS 2043, SEPS 2005, SEPS 2006,are about 70, 70, 17, 29, 32, 50, 1200, and 1220 respectively TypicalBrookfield Viscosity of a 25 weight percent solids solution in tolueneat 25° C. of Kraton D1101, D1116, D1184, D1300X, G1701X, G1702X areabout 4000, 9000, 20000, 6000, 50000 and 50000 cps respectively. TypicalBrookfield Viscosity of a 10 weight percent solids solution in tolueneat 25° C. of G1654X is about 370 cps. The Brookfield Viscosities of a 20and 30 weight percent solids solution in toluene at 30° C. of H-VS-3 areabout 133 cps and 350 cps respectively. Other polymers such as,thermoplastic crystalline polyurethane copolymers with hydrocarbonmidblocks can also be employed.

[0221] The glassy A component type homopolymers can be advantageouslyadded to provide non-tackiness which are selected from one or morehomopolymers of: polystyrene, poly(alpha-methylstyrene),poly(o-methylstyrene), poly(m-methylstryene), poly(p-methylstyrene), andpoly(dimethylphenylene oxide) (GE PPO 612 and Arizona XR 6504). Suchglassy polymers can be use in forming the invention gel, but wouldincrease hot tack.

[0222] The average molecular weight of the glassy homopolymers useful inthe invention gels advantageously can range from about 2,500 to about90,000, typical about 3,000, 4,000, 5,000, 6,000; 7,000; 8,000; 9,000,10,000; 11,000; 12,000, 13,000, 14,000; 15,000; 16,000; 17,000; 18,000;19,000, 20,000; 30,000; 40,000; 50,000; 60,000; 70,000; 80,000; 90,000and the like Example of various molecular weights of commerciallyavailable polystyrene: Aldrich Nos.: 32,771-9 (2,500M_(w)), 32,772-7(4,000 Mw), 37,951-4 (13,000 Mw), 32-774-3 (20,000 Mw), 32,775-1 (35,000Mw), 33,034-5 (50,000 Mw), 32,777-8 (90,000 Mw);poly(alpha-methylstyrene) #41,794-7 (1,300 Mw), 19,184-1 (4,000 Mw);poly(4-methylstyrene) #18,227-3 (72,000 Mw), Endex 155, 160, Kristalex120, 140 from Hercules Chemical, GE: Blendex HPP820, HPP822, HPP823, andthe like.

[0223] Microspheres suitable for use include expanded or unexpanded DE(091-80) phenolic microspheres from Expandcel, Inc. U.S. Especially DE091-80 can be compounded into a masterbatch with polyvinylaciate,polyvinylethylaciate, polyethylevinylaciate, polymethylaciate, and thelike in high concentrations to form strands, pelets, and shapes of anykind which can be configured into regular or irrgular assemblies such asa network, web, lattices and molded with high temperature molten gelthereby expanding the network, web, lattices, and assemblies ofcompounded shapes of masterbatch of expandcel so as to expand in placethe preselected and pre-assebled shaped of expandable foam. In this way,in place foam of any shape and kind are formed in place within theinvention gel or on the surface of the invention gel and the like.

[0224] Suitable triblock copolymers (III) and their typical viscositiesare further described: styrene-ethylene-butylene-styrene blockcopolymers (SEBS) available from Shell Chemical Company and PectenChemical Company (divisions of Shell Oil Company) under tradedesignations Kraton G 1651, Kraton G 1654X, Kraton G 4600, Kraton G 4609and the like. Shell Technical Bulletin SC: 1393-92 gives solutionviscosity as measured with a Brookfield model RVT viscometer at 25° C.for Kraton G 1654X at 10% weight in toluene of approximately 400 cps andat 15% weight in toluene of approximately 5,600 cps. Shell publicationSC:68-79 gives solution viscosity at 25° C. for Kraton G 1651 at 20weight percent in toluene of approximately 2,000 cps. When measured at 5weight percent solution in toluene at 30° C., the solution viscosity ofKraton G 1651 is about 40. Examples of high viscosity SEBS triblockcopolymers includes Kuraray's SEBS 8006 which exhibits a solutionviscosity at 5 weight percent at 30° C. of about 51 cps. Kuraray's 2006SEPS polymer exhibits a viscosity at 20 weight percent solution intoluene at 30° C. of about 78,000 cps, at 5 weight percent of about 27cps, at 10 weight percent of about 1220 cps, and at 20 weight percent78,000 cps. Kuraray SEPS 2005 polymer exhibits a viscosity at 5 weightpercent solution in toluene at 30° C. of about 28 cps, at 10 weightpercent of about 1200 cps, and at 20 weight percent 76,000 cps. Othergrades of SEBS, SEPS, (SEB)_(n), (SEP)_(n) polymers can also be utilizedin the present invention provided such polymers exhibits the requiredhigh viscosity. Such SEBS polymers include (high viscosity) Kraton G1855X which has a Specific Gravity of 0.92, Brookfield Viscosity of a 25weight percent solids solution in toluene at 25° C. of about 40,000 cpsor about 8,000 to about 20,000 cps at a 20 weight percent solidssolution in toluene at 25° C.

[0225] The styrene to ethylene and butylene (S:EB) weight ratios for theShell designated polymers can have a low range of 20:80 or less.Although the typical ratio values for Kraton G 1651, 4600, and 4609 areapproximately about 33:67 and for Kraton G 1855X approximately about27:73, Kraton G 1654X (a lower molecular weight version of Kraton G 1651with somewhat lower physical properties such as lower solution and meltviscosity) is approximately about 31:69, these ratios can vary broadlyfrom the typical product specification values. In the case of Kuraray'sSEBS polymer 8006 the S:EB weight ratio is about 35:65. In the case ofKurary's 2005 (SEPS), and 2006 (SEPS), S:EP weight ratios are 20:80 and35:65 respectively. Much like S:EB ratios of SEBS and (SEB)_(n), the SEPratios of very high viscosity SEPS triblock copolymers are about thesame and can typically vary as broadly.

[0226] The triblock copolymers (III) such as Kraton G 1654X havingratios of 31:69 or higher can be used and do exhibit about the samephysical properties in many respects to Kraton G 1651 while Kraton G1654X with ratios below 31:69 may also be use, but they are lessadvantageous due to their decrease in the desirable properties of thefinal gel.

[0227] The high glassy component copolymers suitable for use in formingthe invention gel include high styrene component BASF's Styroflex senescopolymers including BX 6105 with a statistical SB sequence for the lowelastomeric segments (styrene to butadiene ratio of 1:1) and an overallstyrene content of almost 70%, high styrene content Shell Kraton G,Kraton D-1122X (SB)n, D-4122 SBS, D-4240 (SB)n, D-4230 (SB)n, DX-1150SBS, D-4140 SBS, D-1115 SBS, D-4222 SBS, Kraton D-1401P, SEBS, Dexco'sVector 6241-D, 4411-D, Fina's Finaclear high styrene content SBS seriescopolymers, Phillips Petroleum's XK40 K-Resin styrene/butadienecopolymers, Kuraray's S2104 SEPS The copolymers include amorphouspolymers with high styrene content: SBS, SIS, SEPS, SEB/EPS, and thelike. The copolymers with glassy to elastomeric ratios can range from37:63, 37.6:62.4, 38:62, 39:61, 40:60, 41:59, 42:58, 43:57, 44:65,45:55, 46.54, 47.53, 48.52, 49:51, 50:50, 51:49, 52:48, 53:47, 54:46,55:45, 56:44, 57:43, 58:42, 59:41, 60:40, 6:39, 62:38, 63:37, 64:36,65:35, 66:34, 67:33, 68.32, 69:31, 70:30, 7:29, 72:28, 73:27, 74:26,75:25, 76:24, 77:23, 78:22, 79:21, to 80:20 and higher. High styrenecontent Dow ES30, and ES44 with styrene wt % of 15.7 23.7, 27.3, 28.1,39.6 & 43.9 respectively, M copolymers (ES53, ES58, ES62, ES63, and ES69with styrene wt % of 52.5,58.1, 62.7, 62.8, and 69.2 respectively andcrystallinity, %, DSC, based on copolymer of 37.5, 26.6, 17.4, 22.9,19.6 and 5.0 respectively, S copolymers ES72, ES73, and ES74 withstyrene wt % of 72.7, 72.8, and 74.3 respectively may also be used.These hard to process polymers can be added (from 0.01 to 30 parts byweight) by dry blending in combination with 200-400 parts oil and withSEEPS 4055, 4033, 4077, 4045 and the like and extruded at about between75° C.-135° C. to form a pre-blend and then formulated with additionaloil or/or oil and (I) copolymers to produce the final invention gel.

[0228] Suitable polyolefins include polyethylene and polyethylenecopolymers such as Dow Chemical Company's Dowlex 3010, 2021D, 2038,2042A, 2049, 2049A, 2071, 2077, 2244A, 2267A; Dow Affinity ethylenealpha-olefin resin PL-1840, SE-1400, SM-1300; more suitably: Dow Elite5100, 5110, 5200, 5400, Primacor 141-XT, 1430, 1420, 1320, 3330, 3150,2912, 3340, 3460; Dow Attane (ultra low density ethylene-octene-1copolymers) 4803, 4801, 4602, Eastman Mxsten CV copolymers of ethyleneand hexene (0.905-0.910 g/cm3).

[0229] On the other hand, the molten gelatinous elastomer compositionwill adhere sufficiently to certain plastics (e.g. acrylic, ethylenecopolymers, nylon, polybutylene, polycarbonate, polystyrene, polyester,polyethylene, polypropylene, styrene copolymers, and the like) providedthe temperature of the molten gelatinous elastomer composition issufficient high to fuse or nearly fuse with the plastic. In order toobtain sufficient adhesion to glass, ceramics, or certain metals,sufficient temperature is also required (e.g. above 250° F ).

[0230] The incorporation of such adhesion resins is to provide strongand dimensional stable adherent invention gels, gel composites, and gelarticles. Typically such adherent invention gels can be characterized asadhesive invention gels, soft adhesives or adhesive sealants. Strong andtear resistant adherent invention gels may be formed with variouscombinations of substrates or adhere (attach, cling, fasten, hold,stick) to substrates to form adherent gel/substrate articles andcomposites.

[0231] The present invention gel can also contain useful amounts ofconventionally employed additives such as stabilizers, antioxidants,antiblocking agents, colorants, fragrances, flame retardants, flavors,other polymers in minor amounts and the like to an extend not affectingor substantially decreasing the desired properties. Additives useful inthe gel of the present invention include:tetrakis[methylene3,-(3′5′-di-tertbutyl4″-hydroxyphenyl) propionate]methane, octadecyl 3-(3″,5″-di-tert-butyl-4″-hydroxyphenyl) propionate,distearyl- pentaerythritol-diproprionate, thiodiethylenebis-(3,5-ter-butyl-4-hydroxy) hydrocinnamate,(1,3,5-trimethyl-2,4,6-tris[3,5-di-tert-butyl-4-hydroxybenzyl] benzene),4,4″-methylenebis(2,6-di-tert-butylphenol), Tinuvin P, 123, 144, 213,234, 326, 327, 328, 571, 622, 770, 765, Chimassorb 119, 944, 2020,Uvitex OB, Irganox 245, 1076, 1098, 1135, 5057, HP series: 2215, 2225,2921, 2411, 136, stearic acid, oleic acid, stearamide, behenamide,oleamide, erucamide, N,N″-ethylenebisstearamide,N,N″-ethylenebisoleamide, sterryl erucamide, erucyl erucamide, oleylpalmitamide, stearyl stearamide, erucyl stearamide, calcium sterate,other metal sterates, waxes (e.g. polyethylene, polypropylene,microcrystalline, carnauba, paraffin, montan, candelilla, beeswax,ozokerite, ceresine, and the like). The gel can also contain metallicpigments (aluminum and brass flakes), TiO2, mica, fluorescent dyes andpigments, phosphorescent pigments, aluminatrihydrate, antimony oxide,iron oxides (Fe3O4, —Fe2O3, etc.), iron cobalt oxides, chromium dioxide,iron, barium ferrite, strontium ferrite and other magnetic particlematerials, molybdenum, silicone fluids, lake pigments, aluminates,ceramic pigments, ironblues, ultramarines, phthalocynines, azo pigments,carbon blacks, silicon dioxide, silica, clay, feldspar, glass,microspheres, barium ferrite, wollastonite and the like The report ofthe committee on Magnetic Materials, Publication NMAB-426, NationalAcademy Press (1985) is incorporated herein by reference

[0232] Various glassy phase associating resins having softening pointsabove about 120° C. can also serve as additives to increase the glassyphase of the Invention gel and met the non-tackiness criteria, theseinclude: Hydrogenated aromatic resins (Regalrez 1126, 1128, 1139, 3102,5095, and 6108), hydrogenated mixed aromatic resins (Regalite R125), andother aromatic resin (Picco 5130, 5140, 9140, Cumar LX509, Cumar 130,Lx-1035) and the like.

[0233] The commercial resins which can aid in adhesion to materials(plastics, glass, and metals) may be added in minor amounts to theinvention gels, these resins include: polymerized mixed olefins (SuperSta-tac, Betaprene Nevtac, Escorez, Hercotac, Wingtack, Piccotac),polyterpene (Zonarez, Nirez, Piccolyte, Sylvatac), glycerol ester ofrosin (Foral), pentaerythritol ester of rosin (Pentalyn), saturatedalicyclic hydrocarbon (Arkon P), coumarone indene, hydrocarbon (Picco6000, Regalrez), mixed olefin (Wingtack), alkylated aromatic hydrocarbon(Nevchem), Polyalphamethylstyrene/vinyl toluene copolymer (Piccotex),polystyrene (Kristalex, Piccolastic), special resin (LX-1035), and thelike.

[0234] In my U.S. Pat. No. 5,760,117, is described a non-adhering gelwhich is made non-adhearing, by incorporating an advantage amount ofstearic acid (octadecanoic acid), metal stearates (e.g., calciumstearate, magnesium stearate, zinc stearate, etc.), polyethylene glycoldistearate, polypropylene glycol ester or fatty acid, andpolytetramethylene oxide glycol disterate, waxes, stearic acid andwaxes, metal stearate and waxes, metal stearate and stearic acid. Suchnon-adhering gels by including additives are no longer optical clear andwith time some of the additives blooms uncontrollably to the gelsurface.

[0235] The invention gels are also suitable for forming compositescombinations with various substrates. The substrate materials areselected from the group consisting of paper, foam, plastic, fabric,metal, metal foil, concrete, wood, glass, various natural and syntheticfibers, including glass fibers, ceramics, synthetic resin, andrefractory materials.

[0236] The invention gels can also be made into composites. Theinvention gels can be casted unto various substrates, such as open cellmaterials, metals, ceramics, glasses, and plastics, elastomers,fluropolymers, expanded fluropolymers, Teflon (TFE, PTFE, PEA, FEP,etc), expanded Teflon, spongy expanded nylon, etc.; the molten gelcomposition is deformed as it is being cooled. Useful open-cell plasticsinclude. polyamides, polyimides, polyesters, polyisocyanurates,polyisocyanates, polyurethanes, poly(vinyl alcohol), etc. Open-celledPlastic (sponges) suitable for use with the compositions are describedin “Expanded Plastics and Related Products”, Chemical Technology ReviewNo. 221, Noyes Data Corp., 1983, and “Applied Polymer Science”, OrganicCoatings and Plastic Chemistry, 1975. These publications areincorporated herein by reference.

[0237] The invention gels denoted as “G” can be physically interlockedwith a selected material denoted as “M” to form composites as denotedfor simplicity by their combinations G_(n)G_(n), G_(n)M_(n),G_(n)M_(n)G_(n), M_(n)G_(n)M_(n), M_(n)G_(n)G_(n), G_(n)G_(n)M_(n),M_(n)M_(n)G_(n), M_(n)M_(n)M_(n)G_(n), M_(n)M_(n)M_(n)G_(n)M_(n),M_(n)G_(n)G_(n)M_(n), G_(n)M_(n)G_(n)G_(n), G_(n)M_(n)M_(n)G_(n),G_(n)M_(n)M_(n)G_(n), G_(n)G_(n)M_(n)M_(n), G_(n)G_(n)M_(n)G_(n)M_(n),G_(n)M_(n)G_(n)G_(n), G_(n)G_(n)M_(n), G_(n)M_(n)G_(n)M_(n)M_(n),M_(n)G_(n)M_(n)G_(n)M_(n)G_(n), G_(n)G_(n)M_(n)M_(n)G_(n),G_(n)G_(n)M_(n)G_(n)M_(n)G_(n), and the like or any of theirpermutations of one or more G_(n) with M_(n) and the like, wherein whenn is a subscript of M, n is the same or different selected from thegroup consisting of foam, plastic, fabric, metal, concrete, wood, glass,ceramics, synthetic resin, synthetic fibers or refractory materials andthe like; wherein when n is a subscript of G, n denotes the same or adifferent gel rigidity of from less than about 2 gram to about 1,800gram Bloom and higher).

[0238] Furthermore, the interlocking materials with the gel of theinvention may be made from flexible materials, such as fibers andfabrics of cotton, flax, and silk. Other flexible materials include:elastomers, fiber-reinforced composites, mohair, and wool. Usefulsynthetic fibers include acetate, acrylic, aremid, glass, modacrylicpolyethylene, nylon, olefin, polyester, rayon, spandex, carbon, sufar,polybenzimidazole, and combinations of the above. Useful open-cellplastics include: polyamides, polyimides, polyesters, polyisocyanurates,polyisocyanates, polyurethanes, poly(vinyl alcohol), etc. Open-celledPlastic (foams) suitable for use with the compositions of the inventionare described in “Expanded Plastics and Related Products”, ChemicalTechnology Review No. 221, Noyes Data Corp., 1983, and “Applied PolymerScience”, Organic Coatings and Plastic Chemistry, 1975. Thesepublications are incorporated herein by reference. These include: openand non-opened cell silicone, polyurethane, polyethylene, neoprene,polyvinyl chloride, polyimide, metal, ceramic, polyether, polyester,polystyrene, polypropylene. Example of such foams are: Thanol®, Arcol®,Ugipol®, Arcel®, Arpak®, Arpro®, Arsan®, Dylite®, Dytherm®, Styrofoam®,Trymer®, Dow Ethafoam®, Ensolite®, Scotfoam®, Pyrell®, Volana®,Trocellen®, Minicel®, and the like.

[0239] Sandwiches of gel-material (i.e. gel-material-gel ormaterial-gel-material, etc.) are useful as dental floss, shockabsorbers, acoustical isolators, vibration dampers, vibration isolators,and wrappers. For example the vibration isolators can be use underresearch microscopes, office equipment, tables, and the like to removebackground vibrations. The tear resistance nature of the invention gelsare superior in performance to triblock copolymer gels which are muchless resistance to crack propagation caused by long term continuedynamic loadings.

[0240] Adhesion to substrates is most desirable when it is necessary toapply the adherent invention gels to substrates in the absence of heator on to a low temperature melting point substrate for later peel offafter use, such as for sound damping of a adherent gel composite appliedto a first surface and later removed for use on a second surface. Thelow melting substrate materials which can not be exposed to the highheat of the molten adherent invention gels, such as low melting metals,low melting plastics (polyethylene, PVC, PVE, PVA, and the like) canonly be formed by applying the adherent invention gels to thetemperature sensitive substrates. Other low melting plastics include:polyolefins such as polyethylene, polyethylene copolymers, ethylenealpha-olefin resin, ultra low density ethylene-octene-1 copolymers,copolymers of ethylene and hexene, polypropylene, and etc. Other coldapplied adherent gels to teflon type polymers: TFE, PTFE, PEA, FEP,etc., polysiloxane as substrates are achieved using the adherentinvention gel.

[0241] Likewise, adherent gel substrate composites can be both formed bycasting hot onto a substrate and then after cooling adhering theopposite side of the adherent gel to a substrate having a low meltingpoint. The adherent gel is most essential when it is not possible tointroduce heat in an heat sensitive or explosive environment or in outerspace. The use of solid or liquid resins promotes adherent gel adhesionto various substrates both while the adherent gel is applied hot or atroom temperature or below or even under water. The adherent inventiongels can be applied without heating to paper, foam, plastic, fabric,metal, concrete, wood, wire screen, refractory material, glass,synthetic resin, synthetic fibers, and the like

[0242] The adhesion properties of the invention gels are determined bymeasuring comparable rolling ball tack distance “D” in cm using astandard diameter “d” in mm stainless steel ball rolling off an inclinedof height “H” in cm. Adhesion can also be measured by determining theaverage force required to perform 180° C. peel of a heat formed G₁M₁ oneinch width sample applied at room temperature to a substrate M₂ to formthe composite M₁G₁M₂ The peel at a selected standard rate cross-headseparation speed of 25 cm/minute at room temperature is initiated at theG₁M₂ interface of the M₁G₁M₂ composite, where the substrate M₂ can beany of the substrates mentioned and M₁ preferably a flexible fabric.

[0243] Glassy phase associating homopolymers such as polystyrene andaromatic resins having low molecular weights of from about 2,500 toabout 90,000 can be blended with the triblock copolymers of theinvention in large amounts with or without the addition of plasticizerto provide a copolymer-resin alloy of high impact strengths. Moreadvantageously, when blended with multiblock copolymers andsubstantially random copolymers the impact strengths can be even higher.The impact strength of blends of from about 150 to about 1,500 parts byweight glass phase associating polymer and resins to 100 parts by weightof one or more multiblock copolymers can provide impact strengthapproaching those of soft metals. At the higher loadings, the impactstrength approaches that of polycarbonates of about 12 ft-lb/in notchand higher.

[0244] The invention gel are non tacky to the touch and can bequantified using a simple test by taking a freshly cut Gel probe of aselected gel rigidity made from the invention gel. The gel probe is asubstantially uniform cylindrical shape of length “L” of at least about3.0 cm formed components (1)-(3) of the invention gel in a 16×150 mmtest tube. The gel probe so formed has a 16 mm diameter hemi-sphericaltip which (not unlike the shape of a human finger tip) is brought intoperpendicular contact about substantially the center of the top cover ofa new, un-touched polystyrene reference surface (for example the topcover surface of a sterile polystyrene petri dish) having a diameter of100 mm and a weight of 7.6 gram resting on its thin circular edge (whichminimizes the vacuum or partial pressure effects of one flat surface incontact with another flat surface) on the flat surface of a scale whichscale is tared to zero. The probe's hemi-spherical tip is place incontact with the center of the top of the petri dish cover surface andallowed to remain in contact by the weight of the gel probe while heldin the upright position and then lifted up. Observation is maderegarding the probe's tackiness with respect to the clean referencepolystyrene surface. For purpose of the foregoing reference tack test,tackiness level 0 means the polystyrene dish cover is not lifted fromthe scale by the probe and the scale shows substantially an equalpositive weight and negative weight swings before settling again back tozero with the swing indicated in (negative) grams being less than 1.0gram. A tackiness level of one 1, means a negative swing of greater than1.0 gram but less than 2.0 gram, tackiness level 2, means a negativeswing of greater than 2 gram but less than 3 gram, tackiness level 3,means a negative swing of greater than 3 gram but less than 4 gram,before settling back to the zero tared position or reading. Likewise,when the negative weight swing of the scale is greater than the weightof the dish (i.e., for the example referred above, greater than 7.6gram), then the scale should correctly read −7.6 gram which indicatesthe dish has completely been lifted off the surface of the scale. Suchan event would demonstrate the tackiness of a gel probe havingsufficient tack on the probe surface. The invention gel fails to liftoff the polystyrene reference from the surface of the scale when subjectto the foregoing reference tack test. Advantageously, the invention gelcan register a tackiness level of less than 5, more advantageously, lessthan 3, still more advantageously, less than 2, and still moreadvantageously less than 1. The non-tackiness of the invention gel canadvantageously range from less than 6 to less than 0.5 grams, typicaltack levels are less than 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0,1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.5,2.8, 3.0, 3.5, 4.0, 4.5, 5.0 grams and the like. Whereas probes of gelsmade from amorphous gels such as SEPS, SEBS, S-EP-EB-S, and the likewith copolymer styrene to rubber ratio of less than 37.63 andplasticizer of higher than 30 cSt 40° C. are found to lift thepolystyrene reference from the surface of the scale. For purposes ofindicating tack, the method above can provide gel tack level readings of1, 2, 3, 4, 5, 6, and 7 grams. More accurate and sensitive readings canbe made using electronic scales of tack levels of less than 1 gram. Bythis simple method tack levels (of a gel probe on a polystyrenereference surface) can be measure in terms of gram weight displacementof a scale initially tared to zero For purpose of the present inventionthe method of using a polystyrene reference surface having a weight of7.6 grams in contact and being lifted by the tackiness of a cylindricalgel probe having a 16 mm diameter hemi-spherical tip is used todetermine the tackiness of the invention gel. The level of tack beingmeasured in gram Tack at 23° C.

[0245] Non tacky is defined for the purpose of the invention gel as thefeeling registered in the mind by the sense of touch of the fingers ofthe human hand. An reinforcing observation is that a non tacky referencegel sample does not cling or stick to the fingers under its own weightwhen the force of holding the reference gel sample between the fingersis released and the sample is allowed to fall by the action of gravity.A simple way to accurately measure the non tacky feeling as sensed bythe fingers is to drop a reference gel sample having a cylindrical shapeof about 1.0 cm diameter and 1.0 cm in length a distance of 10 cm on tothe surface of a polystyrene petri dish having a diameter of 10 cminclined at 45°. The reference gel sample is considered non tacky if it(1) “bounce at least twice before coming to rest”, (2) “bounce off”, (3)“bounce and then rolls off”, or (4) “rolls off” on striking thepolystrene surface. If none of (1) thru (4) is observed, then the levelof Gram Tack can be determined by the gel sample method above.

[0246] The invention gel can also contain useful amounts ofconventionally employed additives such as stabilizers, antioxidants,antiblocking agents, colorants, fragrances, flame retardants, otherpolymers in minor amounts and the like to an extend not affecting orsubstantially decreasing the desired properties of the presentinvention.

[0247] The invention gels are prepared by blending together thecomponents (I, II, or III) including the various additives as desired atabout 23° C. to about 100° C. forming a paste like mixture and furtherheating said mixture uniformly to about 150° C. to about 200° C. until ahomogeneous molten blend is obtained. Lower and higher temperatures canalso be utilized depending on the viscosity of the oils and amounts ofmultiblock copolymers (I) and polymer (III) used. These components blendeasily in the melt and a heated vessel equipped with a stirrer is allthat is required Small batches can be easily blended in a test tubeusing a glass stirring rod for mixing. While conventional large vesselswith pressure and/or vacuum means can be utilized in forming largebatches of the instant compositions in amounts of about 40 lbs or lessto 10,000 lbs or more. For example, in a large vessel, inert gases canbe employed for removing the composition from a closed vessel at the endof mixing and a partial vacuum can be applied to remove any entrappedbubbles. Stirring rates utilized for large batches can range from aboutless than 10 rpm to about 40 rpm or higher.

[0248] The invention gel can also contain gases as an additive, i.e. thegel can be foamed. Foam is herein defined as tightly or loosely packingaggregation of gas bubbles, separated from each other by thin or thicklayers of gel. Many types of foamed invention gels (from ultra highdensity to ultra low density) can be produced as desired by (i) addinggas to the molten gel during processing, and (ii) producing gas in themolten get during processing. Gas can be added by whipping a gas intothe molten gel before it cools or introduce a gas into the molten geland then expand or reduce the size of the gas bubbles by reducing thepressure to reduce the bubbles size or applying high pressure to expandthe bubbles size. In this regard, inert gases such as Carbon dioxide,Nitrogen, Helium, Neon, Argon, Krypton, Xenon and Radon are suitable.Air can also be used. Gas can be produced in the molten gel by addingone or more of a “blowing agent” to the Useful blowing agents includedinitroso compounds, such as dinitroso pentamethylene-tetramine,azodicarbonamide, 4,4′oxybis(benzenesulfonyl) hydrazine,5-phenyltetrazole, p-toluenesulfonyl semicarbazide, sulfonyl hydrazide,such as benzene sulfonylhydrazide. Water can be used as a “blowingagent” to ¹ produce varying density of foam invention gels; water usedto advantage can be in the form of mist, droplets, steam, and hot orcold water. The density of the foam invention gels can vary from lessthan 1.00 kilograms per cubic meter to near the solid gel density.Although the materials forming soft solid invention gels may be moreshear resistant, the same materials when made into a foam become muchless shear resistant

[0249] The gel articles can be formed by blending, injection molding,extruding, spinning, casting and other conventional methods. Forexample, Shapes having various crossection can be extruded using aHP-2000 Mixing extruder from Dek-tron Scientific Instruments ofPlainfield, N.J. 07060, USA.

[0250] In general, the basis of this invention resides in the fact thatone or more of a high viscosity linear multiblock and star-shapedmultiblock copolymers (I) or a mixture of two or more of such copolymershaving (A) end block to elastomeric block ratio preferably within thecontemplated range of styrene to rubber ratios of from about 20:80 toabout 40:60 and higher, more preferably from between about 31:69 toabout 40:60 and higher when blended in the melt with an appropriateamount of plasticizing oil makes possible the attainment of inventiongels having a desirable combination of physical and mechanicalproperties, notably high elongation at break of at least 1,600%,ultimate tensile strength of about 8×10⁵ dyne/cm² and higher, lowelongation set at break of substantially not greater than about 2%, tearresistance of 5×10⁵ dyne/cm² and higher, substantially about 100% snapback when extended to 1,200% elongation.

[0251] More specifically, the invention gels of the present inventionexhibit one or more of the following properties. These are: (1) tensilestrength of about 8×10⁵ dyne/cm² to about 10⁷ dyne/cm² and greater; (2)elongation of less than 1,600% to about 3,000% and higher, (3)elasticity modulus of about 10⁴ dyne/cm² to about 10⁶ dyne/cm² andgreater, (4) shear modulus of about 10⁴ dyne/cm² to about 10⁶ dyne/cm²and greater as measured with a 1, 2, and 3 kilogram load at 23° C.; (5)gel rigidity of about less than about 2 gram Bloom to about 1,800 gramBloom and higher; (6) tear propagation resistance of at least about5×10⁵ dyne/cm²; (7) and substantially 100% snap back recovery whenextended at a crosshead separation speed of 25 cm/minute to 1,200% at23° C. Properties (1), (2), (3), and (6) above are measured at acrosshead separation speed of 25 cm/minute at 23° C.

[0252] As the invention gels formed from multiblock copolymers (I)having more and more midblock polymer chains can be expected to exhibitgreater delay recovery form extension or longer relaxation times withincreasing number of midblocks and increasing midblock lengths, suchinvention gels having more than three midblocks forming the copolymers(I) can exhibit extreme tear resistance and excellent tensile strengthwhile at the same time exhibit almost liquid like properties. Forexample, a fun toy can be made from (S-E-EB-E-S), (S-B-EB-EB-S),(S-E-EP-E-EP-S), (S-P-EB-P-EB-S), (S-E-EB-E-EB-E-S),(S-E-EP-E-EP-E-EP-E-S), (S-E-EP-EP)_(n), (S-B-EP-E-EP)_(n),(S-E-EP-E-EP-E)_(n), (S-E-EB-E-EB-E-EB-E-EB-S)_(n) copolymer inventiongels which are molded into cube shapes when placed on the surface of aincline will collect it self together and flow down the incline as amoving body much like a volume of water moving on a high surface tensionsurface. This is due to the greater distance between the end block (A)domains. Such liquid like performing invention gels can be very strongand exhibit extreme tear resistance as exhibited by invention gels madefrom (S-E-EP-S) multiblock copolymer invention gels with shorter (A)distance between domains. Such liquid like invention gels when shapedinto a cube will be deformed by the force of gravity on Earth, but willretain its memory and regain to its molded cube shape when released inouter space or reform into a cube if let loose in a container of liquidof equal density. As a comparison, such a toy formed in the shape of alarge cube from a high viscosity triblock copolymer with a plasticizercontent of 1:1,600 parts will be flattened by the force of gravity andrun down an incline, but is very fragile and will start to tear ifattempt is made to pick it up by hand. This is an excellent comparisonof the difference of tear resistance difference between triblockcopolymer gels and multiblock copolymer invention gels. A usefulapplication is to use such an elastic liquid gel volume to fill acontainer or to encapsulate an electrical or electronic component in acontainer filling every available space, when needed, the shapeless gelvolume can be removed by pouring it out of the container whole.

[0253] The most surprising, unexpected, versatile use of the compositionis dental flossing. The dental floss can be almost any shape so long asit is suitable for dental flossing. A thick shaped piece of thecomposition can be stretched into a thin shape and used for flossing. Athinner shaped piece would require less stretching, etc. For purposes ofdental flossing, while flossing between two closely adjacent teeth,especially between two adjacent teeth with substantial contact pointsand more especially between two adjacent teeth with substantial amalgamalloy metal contact points showing no gap between the teeth, it iscritical that the gel resist tearing, shearing, and crazing while beingstretched to a high degree in such situations. For example, dental gelfloss can take the form of a disk where the segments of thecircumference of the disk is stretched for flossing between the teeth.Other shaped articles suitable for flossing include threads, strips,yarns, tapes, etc., mentioned above.

[0254] In order for invention gels to be useful as a dental floss, itmust overcome the difficult barriers of high shearing and high tearingunder extreme elongation and tension loads. The difficulties that theinvention gels must overcome during flossing can be viewed as follows:during the action of flossing, the gel is stretched from no less thanabout 200% to about 1,100% or higher, the gel floss is deformed as it ispulled down with tearing action between the contacting surfaces of theteeth, then, the wedge of gel floss is sheared between the innercontacting surfaces of the teeth, and finally, the elongated wedged ofgel floss is pulled upwards and out between the surfaces of the teeth.The forces encountered in the act of flossing are: tension, shearing,tearing under extreme tension

[0255] This invention advances the flossing art by providing strong,soft, and extreme tear resistant invention gels made from multiblockcopolymers which invention gels are substantially as soft as the gumssurrounding the teeth.

[0256] The invention gels can also be formed directly into articles orremelted in any suitable hot melt applicator and extruded into shapedarticles and films or spun into threads, strips, bands, yarns, or othershapes using a tubing header, multi-strand header, wire coating header,and the like With respect to various shapes and yarn, its size areconventionally measured in denier (grams/9000 meter), tex (grams/1000meter), and gage (1/2.54 cm). Gage, tex, denier can be converted asfollows: tex=denier/9=specific gravity (2135/gage), for rectangularcross section, tex=specific gravity·(5806×103)(th)(w)/9, where th is thethickness and w the width of the strip, both in centimeters. Generaldescriptions of (1) block copolymers, (2) elastomeric fibers andconventional (3) gels are found in volume 2, starting at pp. 324-415,volume 6, pp 733-755, and volume 7, pp. 515 of ENCYCLOPEDIA OF POLYMERSCIENCE AND ENGINEERING, 1987 which volumes are incorporated herein byreference.

[0257] The invention gels is excellent for cast molding and the moldedproducts have various excellent characteristics which cannot beanticipated form the properties of the raw components. Otherconventional methods of forming the composition can be utilized.

[0258] The high viscosity SEEPS type block copolymers with -E- midblockcan achieve improvements in one or more physical properties includingimproved damage tolerance, improved crack propagation resistance,improved tear resistance, improved resistance to fatigue of the bulk geland resistance to catastrophic fatigue failure of gel composites, suchas between the surfaces of the gel and substrate or at the interfaces ofthe interlocking material(s) and gel, which improvements are not foundin amorphous gels at corresponding gel rigidities.

[0259] As an example, when fabric interlocked or saturated withamorphous S-EB-S gels (gel composites) are used as gel liners for lowerlimb or above the knee prosthesis to reduce pain over pressure areas andgive relief to the amputee, the commonly used amorphous gels forming theliners can tear or rip apart during marathon racewalk after 50-70 miles.In extended use, the amorphous gels can rip on the bottom of the linerin normal racewalk training of 40-60 miles over a six weeks period. Insuch demanding applications, the invention gels are especiallyadvantageous and is found to have greater tear resistance and resistanceto fatigue resulting from a large number of deformation cycles thanamorphous gels. The invention gels are also useful for forming variousorthotics and prosthetic articles such as for lower extremity prosthesisof the L5664 (lower extremity socket insert above knee), L5665 (socketinsert, multi-durometer, below knee), L5666 (below knee, cuff suspensioninterface), L5667 (below knee, above knee, socket insert, suctionsuspension with locking mechanism) type devices as described by theAmerican Orthotic & Prosthetic Association (AOPA) codes. The inventiongels are useful for making AOPA code devices for upper extremityprosthetics. The devices can be cast molded or injection molded incombination with or without fiber or fabric backing or fiber or fabricreinforcement. When such liners are made without fabric backing, variousinvention gels can be used to form gel-gel and gel-gel-gel compositesand the like with varying gel rigidities for the different gel layer(s).

[0260] Health care devices such as face masks for treatment of sleepdisorder require non tacky invention gel. The gel forming a gel overlapportion on the face cup at its edge conforming to the face and serve toprovide comfort and maintain partial air or oxygen pressure when worn onthe face during sleep. Although tacky gels can be made from theinvention gel, tacky gels because of its tactile feel are undesirablefor such applications as face masks and other prolong skin contact uses.

[0261] The invention gel can be formed into gel strands, gel bands, geltapes, gel sheets, and other articles of manufacture in combination withor without other substrates or materials such as natural or syntheticfibers, multifibers, fabrics, films and the like. Moreover, because oftheir improved tear resistance and resistance to fatigue, the inventiongels exhibit versatility as balloons for medical uses, such as balloonfor valvuloplasty of the mitral valve, gastrointestinal balloon dilator,esophageal balloon dilator, dilating balloon catheter use in coronaryangiogram and the like. Since the invention gels are more tearresistant, they are especially useful for making condoms, toy balloons,and surgical and examination gloves. As toy balloons, the invention gelsare safer because it will not rupture or explode when punctured as wouldlatex balloons which often times cause injures or death to children bychoking from pieces of latex rubber. The invention gels areadvantageously useful for making gloves, thin gloves for surgery andexamination and thicker gloves for vibration damping which preventsdamage to blood capillaries in the fingers and hand caused by handlingstrong shock and vibrating equipment. Various other gel articles can bemade from the advantageously tear resistant invention gels and inventiongel composites of the inventions include gel suction sockets, suspensionbelts,

[0262] The invention gels are also useful for forming orthotics andprosthetic articles such as for lower extremity prosthesis describedbelow. Porous, webbing or matting that are skin breathe-able comprisingthe gel strands can be formed into a webs or matting by cold formingsandwiched gel strand-composites using alkyl cyanoacrylates such asethyl, butyl, methyl, propyl cyanoacrylates and the like The alkylcyanoacrylates (AC) will interlock with the soft gelatinous elastomercomposition of the invention, thereby resulting in gel-(AC)-gelcomposite webbing or matting articles Alkyl cyanoacrylates are usefulfor interlocking gel of the invention with other substrates such aspottery, porcelain, wood, metal, plastics, such as acrylics, ABS, EPDM,nylon Fiberglass, phenoics, plexiglass, polycarbonate, polyesters,polystyrene, PVC, urethanes and the like. Other cyanoacrylates such ascyanoacrylate ester are inhibited and do not interlock with theinvention gels.

[0263] In applications where extreme tear resistance, low rigidity, highelongation, good compression set and excellent tensile strength areimportant, the invention gels would be advantageous. The invention gelscan be formed into any desired shaped, size and thickness suitable as acushion; the shaped composition can be additionally surrounded withfilm, fabric, foam, or any other desired material or combinationsthereof. The original shape can be deformed into another shape (tocontact a regular or irregular surface) by pressure and upon removal ofthe applied pressure, the composition in the deformed shape will recoverback to its original shape. A cushion can be made by forming thecomposition into a selected shape matching the contours of the specificbody part or body region. Moreover, the composition can be casted ontosuch materials, provided such materials substantially maintain theirintegrity (shape, appearance, texture, etc.) during the casting process.The same applies for brace cushions for the hand, wrist, finger,forearm, knee, leg, etc.

[0264] Other uses include: shaped articles as toys, optical uses (e.gcladding for cushioning optical fibers from bending stresses) andvarious optical devices, as lint removers, dental floss, as tips forswabs, as soft elastic fishing baits, as a high vacuum seal (againstatmosphere pressure) which contains a useful amount of a mineraloil-based magnetic fluid particles, in the form of (casted, extruded, orspun formed) threads, strips, yarns, strands, tapes which can be weavedinto cloths, fine or coarse fabrics. Still other uses include: games;novelty, or souvenir items; elastomeric lenses, light conducingarticles, optical fiber connectors; athletic and sports equipment andarticles; medical equipment and articles including derma use and for theexamination of or use in normal or natural body orifices, health carearticles; artist materials and models, special effects; articlesdesigned for individual personal care, including occupational therapy,psychiatric, orthopedic, podiatric, prosthetic, orthodontic and dentalcare; apparel or other items for wear by and on individuals includinginsulating gels of the cold weather wear such as boots, face mask,gloves, full body wear, and the like have as an essential, directcontact with the skin of the body capable of substantially preventing,controlling or selectively facilitating the production of moisture fromselected parts of the skin of the body such as the forehead, neck, foot,underarm, etc; cushions, bedding, pillows, paddings and bandages forcomfort or to prevent personal injury to persons or animals; housewaresand luggage; vehicle impact deployable air bag cushions; medical dermause and for the medical examination through surgical orifices of thehuman body, health care articles, artist materials and models, specialeffects, articles designed for individual personal care, includingoccupational therapy, psychiatric, orthopedic, podiatric, prosthetic,orthodontic and dental care, apparel or other items for wear by and onindividuals including insulating invention gels of the cold weather wearsuch as boots, face mask, gloves, full body wear in direct contact withthe skin of the body capable of substantially preventing, controlling orselectively facilitating the production of moisture from selected partsof the skin of the body such as the forehead, neck, foot, underarm, etc;cushions, bedding, pillows, paddings and bandages for comfort or toprevent personal injury to persons or animals, as articles useful intelecommunication, electrical utility, industrial and food processing,in low frequency vibration applications, such as viscoelastic layers inconstrained-layer damping of mechanical structures and goods, asviscoelastic layers used in laminates for isolation of acoustical andmechanical noise, as anti-vibration elastic support for transportingshock sensitive loads, as vibration isolators for an optical table, asviscoelastic layers used in wrappings, enclosures and linings to controlsound, as compositions for use in shock and dielectric encapsulation ofoptical, electrical, and electronic components, as molded shape articlesfor use in medical and sport health care, such use include therapeutichand exercising grips, dental floss, crutch cushions, cervical pillows,bed wedge pillows, leg rest, neck cushion, mattress, bed pads, elbowpadding, dermal pads, wheelchair cushions, helmet liner, cold and hotpacks, exercise weight belts, traction pads and belts, cushions forsplints, slings, and braces (for the hand, wrist, finger, forearm, knee,leg, clavicle, shoulder, foot, ankle, neck, back, rib, etc.), and alsosoles for orthopedic shoes.

[0265] The gel articles molded from the instant compositions havevarious additional important advantages in that they do not crack,creep, tear, crack, or rupture in flexural, tension, compression, orother deforming conditions of normal use, but rather the molded articlesmade from the instant composition possess the intrinsic properties ofelastic memory enabling the articles to recover and retain its originalmolded shape after many extreme deformation cycles.

[0266] The instant compositions can be formed in any shape; the originalshape can be deformed into another shape (to contact a regular orirregular surface) by pressure and upon removal of the applied pressure,the composition in the deformed shape will recover back to its originalshape.

[0267] The invention gels can be made into useful gel articles having noneed for a protective covering, but a protective covering may be use asrequired. Such interlocking with many different materials produce gelcomposites having many additional uses The high tear resistant softinvention gels are advantageously suitable for a safer impact deployableair bag cushions.

[0268] The invention gels are especially suitable and have uses whereresistance to dynamic stretching, shearing and tearing forces areparticularly useful such as those forces acting during fishing asdescribed above and as dental flossing. In the case of dental flossing,freeze dried dental paste can also be incorporated into the gel andformed into dental floss by passing coating the dental floss surfacewith flavors or other agents. Not only is the dental floss a floss, itis an effective tooth brush in between the tooth gap between making it afloss-brush with activated tooth past build in. The gel compounded withtoothpaste can contain any anticavity agents including sodium fluoride,any antigingivitis agents, any whitening agents, and any plaque fightingagents. Freeze dry or powders containing hydrated silica, sorbitol,PVM/MA copolymer, sodium lauryl sulfate, flavor, sodium hydroxide,triclosan, monoammonium phosphate, calcium sulfate, ammonium chloride,magnesium chloride, methylparaben, propylparaben, coloring, and the likecan be compounding into the gel composition forming a floss-brush gelcomposition.

[0269] Gel floss formed from the invention gels has many advantages overconventional dental floss such as regular and extra fine waxed andunwaxed nylon floss, spongy nylon fiber floss, and waxed and unwaxedexpanded and unexpended teflon floss. Such conventional floss are notrecommended for use by children, since a slip or sudden snap in forcingthe floss between the teeth may cause injury to the gums which oftentimes results in bleeding. For sensitive gums and inflamed gums whichhas become red and puffy, it is difficult to floss at, near, and belowthe gumline. The soft gel floss with softness substantially matching thesoftness of the gums are of great advantage for use by children and forflossing teeth surrounded by sensitive and tender gums.

[0270] The shear resistant characteristics of the invention gels can beindirectly determined by subjecting the gel to the shear forces of apair of twisting strings and the resulting inward pulling forces of thetwisting strings can be directly read off of a spring scale As a pair ofstrings are gradually twisted, typical values will range from less thanone pound to fifty pounds and greater. As the string is being twisted(simulating increased shearing forces), the measured pulling forces canrange from a low value of 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30,31 . . . to values of 40, 50, 60, 70, 80 pounds and greater.

[0271] Gel material of low strength can not resist the tremendousshearing action of the twisting strings. The twisting action of thestrings can exhibit a first order twist, a second order twist, or higherorder twists. A first order twist refers to one or more twists of a pairof strings (i.e. a pair of strings when twisted together forms a smalltight binding helix). A second order twist refers to one or more largebinding helixes build up by a pair of strings that have been twistedbeyond the maximum number of twist which normally produce small tightbinding helixes of the first order kind. Similarly, a third order twistrefers to a much larger tightly binding helix build up by the maximumnumber of second order twists produced by the pair of twisting strings.The third order twist may be manifested by the appearance of a branch oftwo or more twist of the first order twisting strings.

[0272] The order of twisting will increase (from a one, two, three, andhigher order twist) until the rubber band breaks. Likewise, a loopedstring with one end attached to a spring scale and the other endattached to a fixed anchor can be twisted into a first, second, third,and higher ordered twist state. This method can be utilized to directlymeasure the force generated for each ordered twist states. The staticforce generated by twisting a string on a spring scale is a way ofdetermining the shear force generated in the shearing action of forcingthe gel floss between two closely contacting teeth when flossing.

[0273] In considering dental flossing criteria, one or more of thefollowing conditions can be regarded as critical factors for dentalflossing gels

[0274] Shear Resistant Criteria

[0275] For the invention gels to be considered useful for flossing, theinvention gels, critically, should withstand a twisting string shearingforce of at least about 5 Kg, more advantageously at least about 8 Kg,and still more advantageously at least about 10 Kg of inward pullingforce of a pair of twisting strings measured directly on a spring scale.

[0276] Flossing Cycle Criteria

[0277] For the invention gels to be considered useful for flossing, theinvention gels, critically, should advantageously be able to perform atleast 4 flossing cycles, more advantageously 8 cycles, and still moreadvantageously of about 20 cycles without breaking apart when a 3.0 mmdiameter gel strand is tested on a set of simulated upper front teethfully contacting under a uniform spring load of (0.9027 Kg) two pounds.The simulated upper front teeth comprises two small stainless steelrollers (⅜″ dia.) facing lengthwise parallel and forced together so asto form a contact length of ½ inches under a spring load of two poundsas measured by a Entran® model ELO-200-4 load cell adjusted by astraight micrometer at room temperature.

[0278] Gel Strength Criteria

[0279] For the invention gels to be considered useful for flossing, theinvention gels, critically, should advantageously exhibit a tensilestrength of at least 5 Kg/cm² (when extended to break as measured at180° U bend around a 5.0 mm mandrel attached to a spring scale) and moreadvantageously at least 8 Kg/cm², and still more advantageously of about10 Kg/cm² and higher. The invention gels useful as dental floss canexhibit tensile strengths at break of at least 20 Kg/cm², moreadvantageously of at least 40 Kg/cm², and exceptionally moreadvantageously at least 60 Kg/cm². Typically, the tensile strengthsrange from about 20 Kg/cm² to about 110 Kg/cm2 and higher, moretypically from about 30 Kg/cm² to 80 Kg/cm² and higher, especially moretypically from about 40 Kg/cm² to about 90 Kg/cm² and higher, andexceptionally typically from about 50 Kg/cm² to about 100 Kg/cm² andhigher.

[0280] Propagatine Tear Criteria

[0281] As a minimum, for the Invention gels to be considered useful forflossing, the invention gels, critically, should advantageously exhibita propagating tear force (when propagating a tear as measured at 180° Ubend around a 5.0 mm diameter mandrel attached to a spring scale) of atleast about 1 Kg/cm, more advantageously at least 2 Kg/cm, and stillmore advantageously of about 3 Kg/cm and higher. The invention gelsuseful as dental floss can exhibit tear strengths of at least 4 Kg/cmand higher, more advantageously of at least 6 Kg/cm and higher,exceptionally more advantageously of at least 8 Kg/cm and higher.Typically, the tear propagation strength can range from about 5 Kg/cm toabout 20 Kg/cm and higher, more typically from about less than 5 Kg/cmto about 25 Kg/cm and higher, especially more typically form about lessthan 6 Kg/cm to about 30 Kg/cm and higher, and exceptionally moretypically from about less than 8 Kg/cm to about 35 Kg/cm and higher.

[0282] For the Invention gels to be considered useful for flossing, theinvention gels, critically, should advantageously exhibit a propagatingtension tear force (when a cylindrical sample is notched and a tear isinitiated at the notched area and propagated past its maximumcylindrical diameter by length-wise stretching of the cylindricalsample) of at least about 1 Kg/cm, more advantageously at least 2 Kg/cm,and still more advantageously of about 4 Kg/cm and higher. The extremetear resistant invention gels typically will exhibit even higher tensiontear values.

[0283] Rigidity Criteria

[0284] The rigidities of the extreme tear resistant useful for flossingcan advantageously range from about 350 gram to about 1,800 gram Bloom,more advantageously from about 400 gram to about 1,500 gram Bloom,especially more advantageously from about 450 gram to about 1,200 gramBloom, still more advantageously from about 450 gram to about 1,000 gramBloom, and less advantageously at values of greater than 1,800 gramBloom.

[0285] In general, as a minimum, the flossing invention gels shouldexhibit several critical properties, including advantageously theability to: (1) withstand a shearing force of at least about 5 Kg underthe string twisting test described above, (2) perform at least 4flossing cycles without breaking apart when tested on a set of simulatedupper front teeth fully contacting under a uniform spring load of twopound, (3) exhibit a tensile strength of at least 5 Kg/cm² and higher,(4) exhibit a propagating tear force at 180° U bend tear test of atleast about 1 Kg/cm, and (5) exhibit a propagating tension tear force(on a notched cylindrical sample) of at least about 1 Kg/cm.

[0286] For use as a dental floss, the gel is made (by extruding,spinning, casting, etc) as a continuous gel strand, the gel strand canbe in the shape of a fiber of a selected diameter (from less than about0.15 to about 5.0 mm and greater) as a continuous tape having a selectedwidth and thickness (less than 0.10 mm thin to about 5.0 mm and thicker)or in any desired shape suitable for flossing. The fiber, tape or aselected shape is then cut to a desired length, rolled up and placedinto a dispenser suitable for containing and dispensing a measured useamount of gel floss. The continuous fiber and tape can be partly cut ornotched for measured single or multiple use When the floss is pulledfrom the dispenser to a point showing the notched or cut mark on thelength of gel floss, the lid is pushed down on the gel floss nipping itand allowing the floss to be further pulled and separated at the notchedor cut point. Additionally, a suitable floss dispenser containing ameasured length of gel floss can be fitted with a cutting edge attachedto its lid or on its body and the uncut and un-notched gel floss can bedispensed from the dispensing container and cut at the desired measureduse length by pressing close the dispenser cutting edge down on thefloss so as to nip and cut the gel or by simply closing the dispenserlid or running the gel along the cutting edge on the dispenser bodyseparating a useful length of gel floss.

[0287] In practice, typically during flossing, a gel strand will undergo various deformations, some of these deformations can be measured,including original shape, extended shape under tension, nipping force,and nipped deformation under a measured force and width. Typically, anyshaped gel strand can be used for flossing, a square cross-section, acircular cross-section, a rectangular cross-section, round, oval, etc.For example, a 2.35 mm diameter strand when extended under a force of2.5 kg can be nipped down to 0.14 mm thickness (along a 3 mm uniformwidth of its cross-section) by a force of 0.9072 Kg (2.0 pound force), areduction of 16.78:1, a 1.89 mm diameter strand when extended under aforce of 2.5 kg can be nipped down to 0.14 mm thickness by a force of0.9072 Kg (2.0 pound force), a reduction of 13.5:1; a 2.75 mm diameterstrand when extended under a force of 2.5 kg can be nipped down to 0.19mm thickness by a force of 0.9072 Kg (2.0 pound force), a reduction of14.4:1; and a 2.63 mm diameter strand when extended under a force of 2.5kg can be nipped down to 0.19 mm thickness by a force of 0.9072 Kg (2.0pound force), a reduction of 13.8:1. the cross-section of the gel flosscan be reduced to any degree by stretching and nipping (from less thanabout 1% to about 1,600% and higher). Advantageously, a gel having therequired strength, tear resistance, gel rigidity, and othercharacteristics described can be formed into a floss of any selectedcross-section and thickness provided the floss is capable of beingstretched when flossing under tension without breaking. Typically thestretching or pulling force is from about less than 0.1 Kg to about 3 Kgand higher. The cross-section of the strand of gel floss should becapable of being nipped by a 0.9027 Kg (2 pounds) force applied across awidth of 3 mm from its original cross-sectional dimensions to a nippedthickness of about 3.0 mm to about 0.02 mm and lower, moreadvantageously from about 2.5 mm to about 0.04 mm and lower, still moreadvantageously from about 2.0 mm to about 0.08 mm and lower; especiallyadvantageously from about 1.5 mm to about 0.15 mm and lower; especiallymore advantageously from about 1.2 mm to about 0.20 mm and lower;especially still more advantageously from about 10 mm to about 0.25 mmand lower.

[0288] The invention gels made from higher viscosity copolymers (I) areresistant to breaking when sheared than triblock copolymer gels. Thiscan be demonstrated by forming a very soft gel, for example 100 partscopolymer to 800 parts plasticizing oil. The soft gel is cut into astrip of 2.5 cm×2.5 cm cross-section, the gel strip is grippedlengthwise tightly in the left hand about its cross-section and anexposed part of the gel strip being gripped lengthwise around itscross-section tightly by the right hand as close to the left hand aspossible without stretching. With the two hands gripping the gel strip'scross-section, the hands are moved in opposite directions to shear apartthe gel strip at its cross-section. The shearing action by the grippinghands is done at the fastest speed possible as can be performed by humanhands. The shearing action is performed at a fraction of a second,possible at about 0.5 seconds. Using this demonstration, the copolymer(I) invention gels will not easily break completely apart as would gelsformed from triblock copolymers. In some cases, it will take two, three,or more attempts to shear a high viscosity copolymer (I) gel strip thisway. Whereas, a lower viscosity triblock copolymer gel strip can besheared apart on the first try. For gels made from copolymers withviscosities of 5 wt % solution in Toluene, their shear resistance willdecrease with decreasing viscosity. For example, the shear strengths astested by hand shearing described above of invention gels made fromcopolymers having polymer viscosities of 150, 120, 110, 105, 95, 90, 89,85, 70, 60, 58, 48, 42, 40, 35, 28, 27, 25, 21 cps, and the like can beexpected to decrease with decreasing viscosity.

[0289] The tensile strengths of multiblock copolymer invention gels madefrom higher viscosity copolymers (I) can be slightly lower than or equalto the tensile strengths of gels made from lower solution viscositytriblock copolymers (III).

[0290] Strands of invention gels comprising higher viscosity multiblockcopolymers will perform better than gel strands made from gels of lowerviscosity triblock copolymers when used in flossing amalgam molars andmore than three times better when used in flossing front teeth.

[0291] Invention gels, in general, will exhibit higher tensile andgreater tear resistance than their parent invention gels containinghigher concentrations of plasticizer. As compared to spongy nylon,regular waxed nylon, and extra fine unwaxed nylon when flossing amalgammolars, the performance of multiblock copolymer invention gels are onthe average substantially better.

[0292] While advantageous components and formulation ranges based on thedesired properties of the multiblock copolymer invention gels have beendisclosed herein. Persons of skill in the art can extend these rangesusing appropriate material according to the principles discussed herein.All such variations and deviations which rely on the teachings throughwhich the present invention has advanced the art are considered to bewithin the spirit and scope of the present invention.

[0293] The invention is further illustrated by means of the followingillustrative embodiments, which are given for purpose of illustrationonly and are not meant to limit the invention to the particularcomponents and amounts disclosed.

[0294] The gels of the invention can be use for making air bags. Theexpansion of the gel air bag is substantially pure volume expansion ordilation as related to K, bulk modulus, y, young's modulus: K=y/3(1−2t),t=3k−2n/6k−2n, where t=poisson's ratio, b=1/k compressibility=−change inV/(V·change in pressure P).

[0295] Surface expansion measure of air bag from initial to expandedstate is from 630 to 833% depending on thickness of original air bag.The initial air bag thickness can vary from 0.5 cm to 10 cms. (0.5, 1,2, 3, 4, 5, 6, 7, 8, 9, 10 cm and higher).

[0296] While advantageous components and formulation ranges based on thedesired properties of the gels have been disclosed herein. Persons ofskill in the art can extend these ranges using appropriate materialaccording to the principles discussed herein. All such variations anddeviations which rely on the teachings through which the presentinvention has advanced the art are considered to be within the spiritand scope of the present invention.

[0297] The invention is further illustrated by means of the followingillustrative embodiments, which are given for purpose of illustrationonly and are not meant to limit the invention to the particularcomponents and amounts disclosed.

EXAMPLE I

[0298] Gels of 100 parts of Kraton G1651, Kraton RP-6917 (amorphousS-EB-S), Septon 8006 (amorphous S-EB-S), Kraton RP-6918, Septon S2006(amorphous S-EP-S) and a high viscosity radial amorphous midblocksegment (SEB)n triblock copolymers and 1,600, 1,200, 1,000, 800, 600,500, 450, 300, 250 parts by weight of Duraprime 200 white oil(plasticizer having Vis. cSt @ 40° C. of 39.0 ) are melt blended, test,and tack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 to 1,800 gram Bloom and the tensile strength,notched tear strength, and resistance to fatigue are found to decreasewith increase amounts of plasticizers, while tackiness of the gels isfound to be greater than 7.6 gram Tack

EXAMPLE II

[0299] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 and 1,600, 1,200, 1,000, 800, 600, 500,450, 300, 250 parts by weight of Duraprime 200 white oil (plasticizerhaving Vis. cSt @ 40° C. of 39.0) are melt blended, test and tack probesamples molded, the bulk gel rigidities are found to be within the rangeof 2 to 1,800 gram Bloom and the gel tackiness are found to increasewith increase amounts of plasticizers and the tack greater than 7.6 gramTack.

EXAMPLE III

[0300] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow S series poly(ethylene/styrene) random copolymer (250,000 Mw)having a high styrene content sufficient to form gel blends with totalstyrene content of 37 by weight of copolymers and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example I, while tack is found todecrease with decreasing plasticizer content and in all instancessubstantially lower than the gels of Example I and II

EXAMPLE IV

[0301] Gels of 100 parts of Septon 4045 (polyethylene containingS-E/EP-S having a styrene content of 37.6) and 1,600, 1,200, 1,000, 800,600, 500, 450, 300, 250 parts by weight of Duraprime Klearol white oil(plasticizer having Vis. CSt @ 40° C. of 7-10) are melt blended, testand probe samples molded, the bulk gel rigidities are found to be withinthe range of 2 to 2,000 gram Bloom and the tackiness is found to be lessthan about 1 gram Tack.

EXAMPLE V

[0302] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof Septon 2104 (Amorphous SEPS having a high styrene content of 65) and800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and tack is found todecrease with decreasing plasticizer content and in all instancessubstantially lower than the gels of Example I and II.

EXAMPLE VI

[0303] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow M series poly(ethylene/styrene) random copolymer (350,000 Mw)having a high styrene content sufficient to form gel blends with totalstyrene content of 37 by weight of copolymers and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example I, while tack is found todecrease with decreasing plasticizer content and in all instancessubstantially lower than the gels of Example I and II.

EXAMPLE VII

[0304] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow E senes poly(ethylene/styrene) random copolymer (240,000 Mw)having a high styrene content sufficient to form gel blends with totalstyrene content of 37 by weight of copolymers and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis CSt @ 40°C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example I, while tack is found todecrease with decreasing plasticizer content and in all instancessubstantially lower than the gels of Example I and II

EXAMPLE VIII

[0305] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with polystyrenehomopolymers (having Mw of 3,000; 4,000; 5,000; 6,000, 7,000; 8,000;9,000; 10,000; 11,000; 12,000, 13,000; 14,000; 15,000; 16,000; 17,000;18,000; 19,000; 20,000; 30,000; 40,000; 50,000; 60,000; 70,000; 80,000;90,000) in sufficient amounts to form gel blends with total styrenecontent of 37, 45, 48, 50, and 55 by weight of copolymers and 800, 600,500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 2,000 gram Bloom and tack is found to decrease withdecreasing plasticizer content and in all instances substantially lowerthan the gels of Example I and II.

EXAMPLE IX

[0306] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow M series poly(ethylene/styrene) random copolymer (350,000 Mw)having a high styrene content sufficient to form gel blends with totalstyrene contents of 40, 45, 48, 50, and 55 by weight of copolymers and800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample I, while tack is found to decrease with decreasing plasticizercontent and in all instances substantially lower than the gels ofExample I and II.

EXAMPLE X

[0307] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow S series poly(ethylene/styrene) random copolymers (with Mw of140,000; 250,000 and 340,000) having a high styrene content sufficientto form gel blends with total styrene content of 40, 45, 48, 50, and 55by weight of copolymers and 800, 600, 500, 450, 300, 250 parts by weightof Duraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70,and 40 (plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I, while tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example I and II.

EXAMPLE XI

[0308] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow E series poly(ethylene/styrene) random copolymers (with Mw of250,000; 340,000 and 400,000) having a high styrene content sufficientto form gel blends with total styrene content of 40, 45, 48, 50, and 55by weight of copolymers and 800, 600, 500, 450, 300, 250 parts by weightof Duraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70,and 40 (plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I, while tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example I and II

EXAMPLE XII

[0309] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow M series poly(ethylene/styrene) random copolymer (with Mw of250,000; 340,000 and 400,000) having a high styrene content sufficientto form gel blends with total styrene content of 40, 45, 48, 50, and 55by weight of copolymers and 800, 600, 500, 450, 300, 250 parts by weightof Duraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70,and 40 (plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I, while tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example I and II.

EXAMPLE XIII

[0310] Gels of 100 parts of Dow E series polyethylene containingpoly(ethylene/styrene) random copolymer (with Mw of 250,000; 340,000 and400,000) having a high styrene content sufficient to form gel blendswith total styrene content of 37, 40, 45, 48, 50, 55, and 60 by weightof copolymers and 800, 600, 500, 450, 300, 250 parts by weight ofDuraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and40 (plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, test, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I, while tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example I and II.

EXAMPLE XIV

[0311] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with polystyrene (of2,500 Mw, 4,000 Mw, 13,000 Mw, 20,000 Mw, 35,000 Mw, 50,000 Mw, and90,000 Mw; poly(alpha-methylstyrene) (of 1,300 Mw, 4,000 Mw;poly(4-methylstyrene)(of 72,000 Mw), Endex 155, 160, Kristalex 120, and140) in sufficient amounts to form gel blends with total styrene contentof 37, 45, 48, 50, and 55 by weight of copolymers and 800, 600, 500,450, 300, 250 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 2,000 gram Bloom and tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example I and II.

EXAMPLE XV

[0312] Examples XIV is repeated and gels of 100 parts of (S-EB₄₅-EP-S),(S-E-EB₂₅-S), (S-EP-E-EP-S), (S-E-EB-S), (S-E-EP-S), (S-E-EP-E-S),(S-E-EP-EB-S), (S-E-EP-E-EP-S), (S-E-EP-E-EB-S), (S-E-EP-E-EP-E-S),(S-E-EP-E-EB-S), (S-E-EP-E-EP-EB-S), and (S-E-EP-E-EP-E-S) blockcopolymers are each melt blended, tests and probe samples molded, thebulk gel rigidities are found to be within the range of 2 to 1,800 gramBloom and tack is found to decrease with decreasing plasticizer contentand in all instances substantially lower than the gels of Example I andII.

EXAMPLE XVI

[0313] Example XIV is repeated and minor amounts of 2, 5, 10 and 15parts of the following polymers are formulated with each of the triblockcopolymers: styrene-butadiene-styrene block copolymers,styrene-isoprene-styrene block copolymers, low viscositystyrene-ethylene-butylene-styrene block copolymers,styrene-ethylene-propylene block copolymers,styrene-ethylene-propylene-styrene block copolymers, styrene-butadiene,styrene-isoprene, polyethyleneoxide, poly(dimethylphenylene oxide),polystyrene, polybutylene, polyethylene, polypropylene, high ethylenecontent EPDM, amorphous copolymers based on2,2-bistrifluoromethyl-4,5-difuoro-1,3-dioxole/tetrafluoroethylene. Thebulk gel rigidities of each of the formulations are found to be withinthe range of 2 gram to 2,000 gram Bloom and tack is found to decreasewith decreasing plasticizer content and in all instances substantiallylower than the gels of Example I and II.

EXAMPLE XVII

[0314] Molten gels of Examples III-XVI are formed into composites withpaper, foam, plastic, elastomers, fabric, metal, concrete, wood, glass,ceramics, synthetic resin, synthetic fibers, and refractory materialsand the resistance to fatigue of the composite-gels at correspondingrigidities are found to be greater than that of the composite-amorphousgels of Example I.

EXAMPLE XVIII

[0315] Three cm thick sheets of each of the gels of Example XIV and theamorphous gels of Example I are tested by repeatedly displacing thesheets to a depth of 1 cm using a 10 cm diameter smooth (water soaked)wood plunger for 1,000, 5,000, 10,000, 25,000, 50,000, and 100,000cycles. The sheets of gels are found capable of exhibiting greaterfatigue resistance than the sheets of amorphous gels at correspondingrigidities.

EXAMPLE XIX

[0316] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow poly(ethylene/styrene) random copolymers ES16 having 37.5%crystallinity and 800, 600, 500, 450, 300, 250 parts by weight ofDuraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and40 (plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I.

EXAMPLE XX

[0317] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow poly(ethylene/styrene) random copolymers ES24 having 26.6%crystallinity and 800, 600, 500, 450, 300, 250 parts by weight ofDuraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and40 (plasticizers having Vis CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I.

EXAMPLE XXI

[0318] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow poly(ethylene/styrene) random copolymers ES27 having 17.4%crystallinity and 800, 600, 500, 450, 300, 250 parts by weight ofDuraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and40 (plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I.

EXAMPLE XXII

[0319] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow poly(ethylene/styrene) random copolymers ES28 having 22.9%crystallinity and 800, 600, 500, 450, 300, 250 parts by weight ofDuraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and40 (plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I.

EXAMPLE XXIII

[0320] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow poly(ethylene/styrene) random copolymers ES30 having 19 6%crystallinity and 800, 600, 500, 450, 300, 250 parts by weight ofDuraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and40 (plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I.

EXAMPLE XXIV

[0321] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow poly(ethylene/styrene) random copolymers ES44 having 5.0%crystallinity and 800, 600, 500, 450, 300, 250 parts by weight ofDuraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and40 (plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I.

EXAMPLE XXV

[0322] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow poly(ethylene/styrene) random copolymers ES72 and 800, 600,500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example I.

EXAMPLE XXVI

[0323] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow poly(ethylene/styrene) random copolymers ES73 and 800, 600,500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example I.

EXAMPLE XXVII

[0324] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow poly(ethylene/styrene) random copolymers ES74 and 800, 600,500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example I.

EXAMPLE XXVIII

[0325] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow poly(ethylene/styrene) random copolymers ES69 and 800, 600,500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example I.

EXAMPLE XXIX

[0326] Gels of 100 parts of Septon polyethylene containing (SEEPS)copolymers 4033, 4055, and 4077 in combination with sufficient amountsof a Dow poly(ethylene/styrene) random copolymers ES62 and 800, 600,500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example I.

EXAMPLE XXX

[0327] Gels of 100 parts of Septon (SEPS) copolymers Kraton GRP6918 incombination with each of a Dow poly(ethylene/styrene) random copolymersES16, ES24, ES27, ES28, ES30, and E544 and 800, 600, 500, 450, 300, 250parts by weight of Duraprime 55, 70, Klearol, Carnation, Blandol, Benol,Semtol 85, 70, and 40 (plasticizers having Vis. CSt @ 40° C. of lessthan 20) are melt blended, tests, and tack probe samples molded, thebulk gel rigidities are found to be within the range of 2 gram to 1,800gram Bloom and the notched tear strength and resistance to fatigue ofthe gel at corresponding rigidities are found to be greater than that ofamorphous gels of Example I.

EXAMPLE XXXI

[0328] Gels of 100 parts of Septon (SEBS) copolymers S8006 and KratonG1651, G1654 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES16, ES24, ES27, ES28, ES30,and ES44 and 800, 600, 500, 450, 300, 250 parts by weight of Duraprime55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40(plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesarc found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I.

EXAMPLE XXXII

[0329] Gels of 100 parts of Septon (SEEPS) copolymers 4033, 4045, 4055,4077 in combination each with 25 parts by weight of Super Sta-tac,Betaprene Nevtac, Escorez, Hercotac, Wingtack, Piccotac, polyterpene,Zonarez, Nirez, Piccolyte, Sylvatac, glycerol ester of rosin (Foral),pentaerythritol ester of rosin (Pentalyn), saturated alicyclichydrocarbon (Arkon P), coumarone indene (Cumar LX), hydrocarbon (Picco6000, Regalrez), mixed olefin (Wingtack), alkylated aromatic hydrocarbon(Nevchem), Polyalphamethylstyrene/vinyl toluene copolymer (Piccotex),polystyrene (Kristalex, Piccolastic), special resin (LX-1035) and 800,600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example I.

EXAMPLE XXXIII

[0330] Gels of 100 parts of Septon (SEEPS) copolymers 4033, 4045, 4055,4077 in combination each with 25 parts by weight of Super Sta-tac,Betaprene Nevtac, Escorez, Hercotac, Wingtack, Piccotac, polyterpene,Zonarez, Nirez, Piccolyte, Sylvatac, glycerol ester of rosin (Foral),pentaerythritol ester of rosin (Pentalyn), saturated alicyclichydrocarbon (Arkon P), coumarone indene (Cumar LX), hydrocarbon (Picco6000, Regalrez), mixed olefin (Wingtack), alkylated aromatic hydrocarbon(Nevchem), Polyalphamethylstyrene/vinyl toluene copolymer (Piccotex),polystyrene (Kristalex, Piccolastic), special resin (LX-1035) and 800,600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example I.

EXAMPLE XXXIV

[0331] A 15 layer rolled/folded gel film actuator having a active musclelength of 10 mm and a diameter of 3 mm (made from 0.5 mm thick Septon4055, 4077, 4045 SEEPS having a 500, 600, 700, 800, 1200, 1600, 1800,2000, 2300, 2500 gram Bloom gel) is found to have a stroke and a forcegreater than actuators made from amorphous SEPS, SEBS gels.

EXAMPLE XXXV

[0332] A 15 layer rolled/folded gel film actuator having a active musclelength of 10 mm and a diameter of 3 mm (made from 0.5 mm thickEthylene-styrene copolymers: ES16, ES24, ES27, ES28, ES28, and ES30having a 500, 600, 700, 800, 1200, 1600, 1800, 2000, 2300, 2500 gramBloom gel) is found to have a stroke and a force greater than actuatorsmade from amorphous SEPS, SEBS gels.

EXAMPLE XXXVI

[0333] A 15 layer rolled/folded gel film actuator having a active musclelength of 10 mm and a diameter of 3 mm (made from 0.5 mm thick made froma 50% of Ethylene-styrene copolymers: ES16, ES24, ES27, ES28, ES28, ES30with a 50% of Septon 4055 having a 500, 600, 700, 800, 1200, 1600, 1800,2000, 2300, 2500 gram Bloom gel) is found to have a stroke and a forcegreater than actuators made from amorphous SEPS, SEBS gels.

EXAMPLE XXXVI

[0334] Unexpanded methacrylonitrile microspheres #051, #053, #091,#091-80, and #092-120 precompounded in masterbatches in the shape ofrods, strands, ropes are configured in 3-D form and expanded in placewith hot gel made from Duraprime 55 white oil in varying amounts toyield oil/microsphere mixtures having the following approximateviscosities (poise): 0.5, 0.8, 1.5, 18, 34, 100, 150, 250, 400, 460,480, 560, 720, 1000, and 2000.

EXAMPLE XXXVI

[0335] Unexpanded methacrylonitrile microspheres #051, #053, #091,#091-80, and #092-120 precompounded in masterbatches in the shape offibers, haris, ficrofibers, threads, are configured in 3-D form andexpanded in place with hot gel made from Duraprime 70 white oil invarying amounts to yield oil/microsphere mixtures having the followingapproximate viscosities (poise): 0.5, 0.8, 1.5, 18, 34, 100, 150, 250,400, 460, 480, 560, 720, 1000, and 2000.

EXAMPLE XXXVI

[0336] Unexpanded methacrylonitrile microspheres #051, #053, #091,#091-80, and #092-120 precompounded in masterbatches in the shape ofsolid sphere, rod, cone, regular and irregular shapes are configured in3-D form and expanded in place with hot gel made from Duraprime 90 whiteoil in varying amounts to yield oil/microsphere mixtures having thefollowing approximate viscosities (poise): 0.5, 0.8, 1.5, 18, 34, 100,150, 250, 400, 460, 480, 560, 720, 1000, and 2000.

EXAMPLE XXXVI

[0337] Unexpanded methacrylonitrile microspheres #051, #053, #091,#091-80, and #092-120 precompounded in masterbatches in the shape ofsheets are configured in 3-D form and expanded in place with hot gelmade from Duraprime 200 white oil in varying amounts to yieldoil/microsphere mixtures having the following approximate viscosities(poise): 0.5, 0.8, 1.5, 18, 34, 100, 150, 250, 400, 460, 480, 560, 720,1000, and 2000

[0338] While preferred components and formulation ranges have beendisclosed herein persons of skill in the art can extend these rangesusing appropriate material according to the principles discussed herein.Furthermore, Polyethylene containing midblock segment block polymers canbe use in blending with other engineering plastics and elastomericpolymers to make alloyed compositions having improved impact and tearresistance properties. All such variations and deviations which rely onthe teachings through which the present invention has advanced the artare considered to be within the spirit and scope of the presentinvention.

What I claim is:
 1. A artificial muscle actuator comprising: a) one ormore thin film layers folded or rolled into the shape of a cylinderforming a center part of said cylinder and an outer part of saidcylinder, said film layer having a top surface M_(n1) and a bottomsurface M_(n2), said top surface and said bottom surface each coatedwith an electrical conducting layer M_(c), said conducting layer of saidtop surface connected by a first electrode on said top surfacepositioned at said center part and said bottom surface connected by asecond electrode on said bottom surface positioned at said outer part;said first and second electrodes being connected to one or more directcurrent power source or sources, said power supply capable of generatinga electrical potential of a positive electrical charge to the firstelectrode and a negative electrical charge to the second electrode fromless than about 100 volt to above about 10,000 volts; said film layerscomprising a gel made from one or more copolymers having one or morepolyethylene segments and capable of exhibiting crystanility at about10° C. and higher as determined by DSC curve, said gel having rigiditiesof from less than about 2 gram Bloom to about 1,800 gram Bloom; and saidgel being capable of exhibiting greater tear resistance than amorphousgels of SEPS and SEBS.
 2. A artificial muscle actuator comprising: a)one or more thin film layers folded or rolled into the shape of acylinder forming a center part of said cylinder and an outer part ofsaid cylinder, said film layer having a top surface and a bottomsurface, said top surface and said bottom surface each coated with anelectrical conducting layer, said conducting layer of said top surfaceconnected by a first electrode on said top surface positioned at saidcenter part and said bottom surface connected by a second electrode onsaid bottom surface positioned at said outer part; said first and secondelectrodes being connected to a direct current power source, said powersupply capable of generating a electrical potential of a positiveelectrical charge to the first electrode and a negative electricalcharge to the second electrode of about 100 v, 200 v, 300 v, 400 v, 500v, 600, 700 v, 800, 900, 1,000 v, 2,000 v, 3,000 v, 4,000 v, 5,000 v,6,000 v, 7,000 v, 8,000 v, 9,000 v, 10,000 v, 11,000 v, 12,000 v,15,000v and higher; said film layers comprising a gel made from one or morecopolymers in combination with or without polyphenylene ether, saidcopolymers having one or more polyethylene segments; and said copolymerscapable of exhibiting crystanility at about 10° C. and higher asdetermined by DSC curve, said gel having rigidities of from less thanabout 2 gram Bloom to about 1,800 gram Bloom; and said gel being capableof exhibiting greater tear resistance than amorphous gels of SEPS andSEBS.
 3. A artificial muscle actuator comprising: a) one or more thinfilm layers folded or rolled into the shape of a cylinder forming acenter part of said cylinder and an outer part of said cylinder, saidfilm layer having a top surface and a bottom surface, said top surfaceand said bottom surface each coated with an electrical conducting layer,(E), said conducting layer of said top surface connected by a firstelectrode on said top surface positioned at said center part and saidbottom surface connected by a second electrode on said bottom surfacepositioned at said outer part; said first and second electrodes beingconnected to a direct current power source, said power supply capable ofgenerating a electrical potential of a positive electrical charge, tothe first electrode and a negative electrical charge, to the secondelectrode of at least about 10,000 volts; said film layers comprising acomposite of one or more gel, G, film layers and one or more electrode,E, coating layers, said composite selected from EGE, EGEGE, EGEGEGE,EGEGEGEGE, and EGEGEGEGEGE; said film layers comprising a gel made fromone or more copolymers in combination with or without polyphenyleneether, said copolymers having one or more polyethylene segments; andsaid copolymers capable of exhibiting crystanility at about 10° C. andhigher as determined by DSC curve, said gel having rigidities of fromless than about 2 gram Bloom to about 1,800 gram Bloom; and said gelbeing capable of exhibiting greater tear resistance than amorphous gelsof SEPS and SEBS.